阅读说明：本技术 处理液组合物、喷墨印染组合物组、喷墨印染方法及布帛 (Treatment liquid composition, ink jet printing composition set, ink jet printing method, and fabric ) 是由 宫佐亮太 大桥正和 于 2019-07-30 设计创作，主要内容包括：提供一种提高了显色性且粘度良好的处理液组合物、喷墨印染组合物组、喷墨印染方法及布帛。处理液组合物是附着在布帛上使用的处理液组合物,含有阳离子性化合物、水溶性树脂和水,处理液组合物包含的水溶性成分的分子量分布,在分子量为2.8万至280万的范围具有极大值,分子量为2.8万至280万的水溶性树脂的含量相对于处理液组合物的总量为0.6质量％至5.0质量％。(Provided are a treatment liquid composition having improved color developability and good viscosity, an inkjet printing composition set, an inkjet printing method, and a fabric. The treatment liquid composition is used by being adhered to a fabric, and contains a cationic compound, a water-soluble resin and water, wherein the molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum value in a range of molecular weight of 2.8 to 280 ten thousand, and the content of the water-soluble resin having a molecular weight of 2.8 to 280 ten thousand is 0.6 to 5.0 mass% with respect to the total amount of the treatment liquid composition.)

1. A treatment liquid composition characterized by comprising,

the treatment liquid composition is used by adhering to a fabric,

the treatment liquid composition contains a cationic compound, a water-soluble resin and water,

the molecular weight distribution of the water-soluble component contained in the treatment liquid composition has a maximum value in the range of 2.8 to 280 ten thousand molecular weight,

the content of the water-soluble resin having a molecular weight of 2.8 to 280 ten thousand is 0.6 to 5.0 mass% with respect to the total amount of the treatment liquid composition.

2. The treatment liquid composition according to claim 1,

the molecular weight distribution of the water-soluble component further has a maximum value in the range of molecular weight of 1000 to 2.5 ten thousand,

the ratio of the peak area having a molecular weight of 2.8 to 280 ten thousand to the peak area having a molecular weight of 1000 to 2.5 ten thousand is 1:5 to 5: 1.

3. The treatment liquid composition according to claim 1 or 2,

the water-soluble resin is selected from more than one of polyoxyethylene, carboxymethyl cellulose, hydroxyethyl cellulose and polyvinylpyrrolidone.

4. The treatment liquid composition according to claim 1,

the treating fluid composition further contains a water-repellent agent,

the content of the water repellent is 0.01 to 0.30% by mass relative to the total amount of the treatment liquid composition.

5. The treatment liquid composition according to claim 4,

the water repellent is one or more selected from fluorine water repellent, silicone water repellent, and paraffin wax.

6. The treatment liquid composition according to claim 4 or 5,

the waterproof agent is resin with a melting point below 100 ℃.

7. The treatment liquid composition according to claim 1,

the fabric is polyester or a blend of polyester and cotton.

8. The treatment liquid composition according to claim 1,

the fabric is a fabric having a colored portion, and the L value of the colored portion is 80 or less.

9. The treatment liquid composition according to claim 1,

the treatment liquid composition further contains resin particles.

10. The treatment liquid composition according to claim 1,

the treatment liquid composition further contains a nonionic surfactant,

the nonionic surfactant is a polyoxyethylene oleyl ether.

11. The treatment liquid composition according to claim 1,

the cationic compound is a polyvalent metal salt,

the polyvalent metal salt is one or more selected from calcium nitrate, calcium chloride and magnesium sulfate.

12. The treatment liquid composition according to claim 1,

the treating fluid composition is used for ink jet pigment printing and dyeing.

13. A set of ink jet printing compositions comprising:

the treatment liquid composition according to any one of claims 1 to 12; and

a pigment printing ink jet ink composition containing a pigment, resin particles and water.

14. The set of ink jet printing compositions of claim 13,

the pigment printing ink jet ink composition is a white ink containing a white pigment.

15. An ink-jet textile printing method characterized in that,

the method comprises a treatment liquid composition adhesion step of adhering the treatment liquid composition according to any one of claims 1 to 12 to the fabric.

16. The ink jet printing method according to claim 15, wherein,

the method comprises an ink composition adhesion step of adhering a pigment printing ink jet ink composition containing a pigment, resin particles and water to a region to which the treatment liquid composition adheres, after the treatment liquid composition adhesion step.

17. A fabric characterized in that,

the fabric to which the treatment liquid composition according to any one of claims 1 to 12 is attached.

Technical Field

The invention relates to a treatment liquid composition, an inkjet textile printing composition set, an inkjet textile printing method, and a fabric.

Background

Conventionally, in the production of a printed material by dyeing a substrate such as a fabric with a color material, a technique of pretreating the substrate with a treatment liquid containing a cationic compound or the like is known in order to improve the color developability of the color material. For example, patent document 1 proposes a pretreatment agent for ink jet textile printing, which contains a water-soluble polyvalent metal salt and a specific resin emulsion as such a treatment liquid.

However, in recent years, there has been a demand for a dye in ink jet textile printing to have higher color developability, and the treatment liquid described in patent document 1 has a problem that the color developability cannot be sufficiently improved. In addition, there is a problem that if the content of the water-soluble polyvalent metal salt or the specific resin emulsion in the treatment liquid is increased in order to improve the color developability of the color material in the printed matter, the viscosity of the treatment liquid tends to be increased.

Patent document

Patent document 1: japanese patent laid-open No. 2008-266853.

Disclosure of Invention

Accordingly, several aspects of the present invention are directed to provide a treatment liquid composition, an inkjet textile printing composition set, an inkjet textile printing method, and a fabric, which can solve the above problems and obtain a printed textile having good viscosity and excellent color developability.

The treatment liquid composition of the present invention is a treatment liquid composition for use as being adhered to a fabric, and contains a cationic compound, a water-soluble resin, and water, wherein a molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum value in a range of a molecular weight of 2.8 to 280 ten thousand, and a content of the water-soluble resin having a molecular weight of 2.8 to 280 ten thousand is 0.6 to 5.0 mass% with respect to a total amount of the treatment liquid composition.

In the above treatment liquid composition, it is preferable that the molecular weight distribution of the water-soluble component further has a maximum value in a range of a molecular weight of 1000 to 2.5 ten thousand, and a ratio of a peak area of 2.8 to 280 ten thousand in molecular weight to a peak area of 1000 to 2.5 ten thousand in molecular weight is 1:5 to 5: 1.

In the treatment liquid composition, the water-soluble resin is preferably at least one selected from the group consisting of polyoxyethylene, carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl pyrrolidone.

The treatment liquid composition preferably further contains a water repellent in an amount of 0.01 to 0.30% by mass based on the total amount of the treatment liquid composition.

The water repellent is preferably at least one member selected from the group consisting of fluorine-based water repellent, silicone-based water repellent, and paraffin wax.

The water repellent is preferably a resin having a melting point of 100 ℃ or lower.

In the treatment liquid composition, the fabric is preferably polyester or a blend of polyester and cotton.

Preferably, the treatment liquid composition is a fabric having a colored portion, and the L value of the colored portion is 80 or less.

The treatment liquid composition preferably further contains resin particles.

The above treatment liquid composition further contains a nonionic surfactant, and preferably the nonionic surfactant is polyoxyethylene oleyl ether.

In the treatment liquid composition, the cationic compound is preferably a polyvalent metal salt, and the polyvalent metal salt is one or more selected from the group consisting of calcium nitrate, calcium chloride and magnesium sulfate.

The above-mentioned treatment liquid composition is preferably used for ink jet pigment printing.

The ink jet textile printing composition set of the present invention includes the above treatment liquid composition and a pigment textile printing ink jet ink composition containing a pigment, resin particles and water.

In the ink jet textile printing composition set, the pigment textile printing ink composition is preferably a white ink containing a white pigment.

The ink jet textile printing method of the present invention includes a treatment liquid composition adhesion step of adhering the treatment liquid composition to a fabric.

The ink jet textile printing method preferably includes an ink composition adhesion step of adhering a pigment textile printing ink composition containing a pigment, resin particles, and water to a region to which the treatment liquid composition adheres, after the treatment liquid composition adhesion step.

The fabric of the present invention is a fabric to which the treatment liquid composition is attached.

Drawings

Fig. 1 is a schematic perspective view showing an inkjet textile printing apparatus according to an embodiment.

Description of the reference numerals

1 … … printer; 2 … … cloth; 3 … … ink jet head; 4 … … bracket; 5 … … main scanning mechanism; 6 … … impression roller; 7a, 7b, 7c, 7d, 7e, 7f … … ink cartridges; 8 … … synchronous belts; 9 … … a motor; 10 … … guide the shaft.

Detailed Description

Hereinafter, embodiments of the present invention will be described. The embodiment described below is an example of the present invention. The present invention is not limited to the following embodiments, and can be modified as appropriate within a range not departing from the spirit or concept of the invention as interpreted from the claims and the entire specification, and a treatment liquid composition, an inkjet printing composition set, an inkjet printing method, and a fabric to which such modifications are applied are also included in the technical scope of the present invention.

Treatment liquid composition

The treatment liquid composition according to the present embodiment (hereinafter also simply referred to as "treatment liquid") is a treatment liquid composition used for adhering to a fabric, and contains a cationic compound, a water-soluble resin, and water. In addition, the molecular weight distribution of the water-soluble component contained in the treatment liquid composition has a maximum value in the range of 2.8 ten thousand (2 ten thousand 8 thousand) to 280 ten thousand in molecular weight, and the content of the water-soluble resin having a molecular weight of 2.8 ten thousand to 280 ten thousand is 0.6% by mass to 5.0% by mass with respect to the total amount of the treatment liquid composition.

The treatment liquid composition according to the present embodiment is preferably used by being attached to a fabric, which is a base material of a printed material, in advance when the ink composition is attached to the fabric to produce the printed material. The ink composition described later can be used. In particular, when the pigment printing ink jet ink composition is used as an ink composition, the pigment is easily retained on the surface of the fabric by the treatment liquid composition according to the present embodiment. This makes it possible to improve the color developability of the pigment in the printed material. Therefore, the treatment liquid composition according to the present embodiment is preferably a treatment liquid composition for pigment printing, and more preferably a treatment liquid composition for inkjet pigment printing.

Hereinafter, each component contained in the treatment liquid composition according to the present embodiment will be described. Hereinafter, an ink composition used for producing a printed material will be described as an example of a pigment printing ink jet ink composition (hereinafter, also simply referred to as "ink composition").

Cationic compound

The treatment liquid composition according to the present embodiment contains a cationic compound. The cationic compound has a function of aggregating components in the ink composition. That is, when the ink composition is attached to the fabric to which the treatment liquid is attached in the production of the printed matter, the cationic compound contained in the treatment liquid acts on the particles such as the pigment or the resin particles (emulsion) contained in the ink composition. This promotes aggregation between the particles, and suppresses absorption into the gaps or the interior of the fibers constituting the fabric. Therefore, the color development of the pigment (color material) in the printed matter can be improved. The cationic compound also has a function of increasing the viscosity of the ink composition. Therefore, excessive penetration of the ink composition into the fabric can be suppressed, and occurrence of bleeding or oozing can be reduced.

The function of the cationic compound is derived from the action of neutralizing the surface charge of the components contained in the ink composition or changing the pH of the ink composition. These actions can aggregate or precipitate a pigment or the like in the ink composition, or thicken the ink composition.

Examples of the cationic compound include polyvalent metal salts and cationic resins. Among them, polyvalent metal salts are preferably used from the viewpoint of improving the color developability of the pigment and being suitable for cotton cloth and polyester cloth. These cationic compounds may be used alone or in combination of two or more.

The polyvalent metal salt is a compound containing a polyvalent metal cation of divalent or higher and an anion forming a salt with the polyvalent metal cation, and having water solubility. Examples of the divalent or higher polyvalent metal cation include: such as Ca ²⁺、Cu ²⁺、Ni ²⁺、Mg ²⁺、Zn ²⁺、Ba ²⁺Divalent metal ions; al (Al) ³⁺、Fe ³⁺、Cr ³⁺And (4) trivalent metal ions are obtained. Examples of the anion include: for example Cl ^-、I ^-、Br ^-、SO ₄ ^2-、CO ₃ ^2-、ClO ₃ ^-、NO ₃ ^-、HCOO ^-、CH ₃COO ^-And the like. Among such polyvalent metal salts in which polyvalent metal cations and anions are combined, calcium salts or magnesium salts are preferably used from the viewpoint of improving the storage stability of the treatment liquid and the color developability expressed by the aggregation action on the pigment and the resin particles (emulsion). Examples of suitable calcium salts and magnesium salts include calcium nitrate, calcium chloride, and magnesium sulfate, and one or more selected from them can be used. In particular, calcium salt is more preferably used from the viewpoint of a strong agglutination and further improvement in color developability.

The polyvalent metal salt may be hydrate. As the hydrate of calcium chloride, for example, calcium chloride 2 hydrate; as the hydrate of calcium nitrate, for example, calcium nitrate 4 hydrate can be used. One polyvalent metal salt may be used alone, or two or more kinds may be used in combination. In the case of using two or more polyvalent metal salts in combination, it is preferable to use a calcium salt and a magnesium salt in combination. In this case, the aggregation action on the pigment and the resin particles (emulsion) can be easily controlled. Since the aggregation can be prevented from being excessively strong, graininess of an image is less likely to occur in a printed matter, and as a result, color unevenness of the image can be reduced. Magnesium sulfate is preferably used as the magnesium salt.

The cationic compound may be a metal salt other than the polyvalent metal salt, in addition to the polyvalent metal salt. An example of such a metal salt is a combination of Na ^-、K ^-Sodium sulfate, potassium sulfate, etc. as monovalent metal cations and the anions described above.

Examples of the cationic resin include: for example, cationic urethane resins, olefin resins, and allylamine resins.

As the cationic polyurethane resin, a known resin or a commercially available product can be used. The cationic polyurethane resin may be any of a resin dissolved in a solvent such as water or an organic solvent, a resin dispersed in the solvent to form an emulsion, and the like. Examples of such cationic polyurethane resin include: for example, Hydran (registered trademark) CP-7010, 7120, 7030, 7040, 7050, 7060, 7610 (trade name, japan ink chemical industry, inc.), Superflex (registered trademark) 600, 610, 620, 630, 640, 650 (trade name, first industrial pharmaceutical company, inc.), polyurethane emulsion WBR-2120C, 2122C (trade name, university fine chemical company, inc.), and the like.

The cationic olefin resin is a polymer compound derived from an olefin monomer and having a structure such as an ethylene chain or a propylene chain as a main skeleton. The cationic olefin-based resin may be a known resin or a commercially available product, or may be a resin dissolved in a solvent such as water or an organic solvent, or a resin dispersed in the solvent to form an emulsion. Examples of such cationic olefin-based resins include: for example, ARROWBASE (registered trademark) CB-1200, CD-1200 (trade name, Unitika, supra), and the like.

As the cationic allylamine-based resin, known resins can be used, for example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polydiallylamine amide sulfate, polydiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylammonium ethylsulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, polyallylamine hydrochloride-diallyl sulfate copolymer, polyallylamine hydrochloride-sulfur dioxide copolymer, polyallylamine hydrochloride-diallyl ammonium chloride copolymer, polyallylamine hydrochloride-diallyl sulfate copolymer, diallyl dimethyl ammonium chloride sulfur dioxide copolymer, diallyl dimethyl ammonium chloride acrylamide copolymer and the like.

As such cationic allylamine-based resins, commercially available products such as PAA-HCL-01, 03, 05, 3L, and 10L; PAA-H-HCL; PAA-SA; PAA-01, 03, 05, 08, 15C, 25; PAA-H-10C; PAA-D11-HCL; PAA-D41-HCL; PAA-D19-HCL; PAS-21CL, 22SA, 92A; PAS-M-1, 1L, 1A; PAS-H-1L, 5L, 10L; PAS-J-81, 81L (trade name, Nittobo pharmaceutical Co., Ltd., supra), Hymoloc (registered trademark) NEO-600, Q-101, Q-311, Q-501, HI-MACS SC-505 (trade name, Hymo corporation, supra), and the like.

In addition to the cationic resin or polyvalent metal salt, a cationic surfactant, an inorganic acid, an organic acid, or the like may be used as another cationic compound.

Examples of the cationic surfactant include: examples of the salt include primary amines, secondary amines, tertiary amine salt compounds, alkylammonium salts, dialkylammonium salts, aliphatic ammonium salts, benzalkonium salts, quaternary ammonium salts, alkylammonium salts, alkylpyridinium salts, sulfonium salts, phosphonium salts, onium salts, and imidazolinium salts. Specific examples of such a cationic surfactant include: for example, hydrochloride or acetate salts of laurylamine, cocoamine, rosin amine, etc.; dodecyl trimethyl ammonium chloride (lauryl trimethyl ammonium chloride), hexadecyl trimethyl ammonium chloride (cetyl trimethyl ammonium chloride), benzyl tributyl ammonium chloride, benzalkonium chloride, dimethylethyl lauryl ammonium ethyl sulfate, dimethylethyl octyl ammonium ethyl sulfate, trimethyl lauryl ammonium hydrochloride, hexadecyl pyridine chloride, hexadecyl pyridine bromide, dihydroxyethyl lauryl amine, 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. Commercially available products of these cationic surfactants can be used.

Examples of the inorganic acid or organic acid include: inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; organic acids such as 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, orthophosphoric acid, pyrrolidone carboxylic acid, pyran carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumarin acid, thiophene carboxylic acid, and nicotine acid, and derivatives or salts thereof of these compounds. These may be used alone or in combination of two or more.

As other cationic compounds, it is possible to use, for example: inorganic pigments such as chalk, kaolin, calcined clay, talc, titanium oxide, zinc sulfide, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, calcium montmorillonite, sodium montmorillonite, bentonite, and the like; acrylic plastic pigments; organic pigments such as urea polymers.

The content of the cationic compound contained in the treatment liquid is not particularly limited, but is preferably 0.1 mass% or more and 40.0 mass% or less, more preferably 2.0 mass% or more and 25.0 mass% or less, further preferably 3.0 mass% or more and 15.0 mass% or less, and particularly preferably 5.0 mass% or more and 10.0 mass% or less with respect to the total amount of the treatment liquid. When the content of the cationic compound is within the above range, precipitation, separation, or the like of the cationic compound in the treatment liquid is suppressed, aggregation of the pigment or the resin particles (emulsion) in the ink composition is promoted, and entry into the gaps or the inside of the fibers constituting the fabric is suppressed. In this way, the filling effect of the components such as the ink composition staying in the vicinity of the surface of the fabric can reduce the phenomenon (strike-through) in which the pigment (coloring material) penetrates in the direction of the back surface of the printing surface, and can improve the color developability of the pigment in the printed material.

Water-soluble resin

The treatment liquid composition according to the present embodiment contains a water-soluble resin. By containing the water-soluble resin, molecular chains of the water-soluble resin are likely to entangle with fibers of the fabric, and the viscosity of the treatment liquid composition tends to be relatively increased. Thus, the water-soluble resin has a function of allowing the treatment liquid composition to easily remain on the surface of the fabric when the treatment liquid composition is adhered. In particular, since fibers of the polyester fabric are less hydrophilic than cotton, an aqueous treatment liquid composition or an aqueous ink composition is easily repelled by the fibers of the polyester. Therefore, the treatment liquid composition tends to be more difficult to fix to the fibers in the polyester fabric than in the cotton fabric. On the other hand, by containing the water-soluble resin composition, the treatment liquid composition can be more favorably retained on the surface of the fabric.

In addition, in order to improve air permeability, the polyester fabric is generally formed to have a relatively large (coarse) mesh, and therefore the ink composition may be more likely to sink into the interior of the fabric. In contrast, by containing the water-soluble resin composition, the treatment liquid composition can be more favorably retained on the surface of the fabric. Further, when the ink composition is attached to the fabric to which the treatment liquid composition is attached, the water-soluble resin is dissolved in the ink composition, and the viscosity of the ink composition is increased. The increase in viscosity reduces the fluidity of the ink composition, and the ink composition is less likely to sink into the fabric and easily stay on the surface of the fabric. As a result, the ink composition stays on the surface of the fabric, and favorable color development can be obtained.

Examples of the water-soluble resin include nonionic resins, anionic resins, and cationic resins. In the present specification, the cationic resin is suitable for both the cationic compound and the water-soluble resin.

In the present specification, "water-soluble" refers to a characteristic of being soluble in ion-exchanged water at 20 ℃ by 3 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 25 mass% or more.

The water-soluble resin preferably contains at least one selected from the group consisting of polyethylene oxide, carboxymethyl cellulose, hydroxyethyl cellulose, and polyvinyl pyrrolidone. Among them, polyethylene oxide and polyvinylpyrrolidone, which are nonionic resins, are preferable, and polyvinylpyrrolidone is more preferable. The polyvinylpyrrolidone is more easily dissolved in the ink composition, so that the viscosity of the ink composition is increased and the color development is easily improved. Further, polyvinylpyrrolidone has low tow property, and thus the treatment liquid composition can be easily applied well.

As polyethylene oxide (hereinafter, also referred to as polyoxyethylene), commercially available products can be used, and examples thereof include PEO (registered trademark) -1, 2,3, 4, 8, 15, 18, 27, and 29 (above, trade names, sumitomo chemical corporation); alkox (registered trademark) L-6, L-8, L-11, E-30, E-45, E-60, E-75, E-100, E-160, E-240, E-300, R-150, R-400, R-1000 (trade name, Mingcheng chemical industry Co., Ltd.) and the like.

In addition, as the polyoxyethylene, there is no limitation to homopolymers, and for example, copolymers of ethylene oxide with other monomers, such as copolymers of ethylene oxide and propylene oxide, may also be used.

The weight average molecular weight of the polyoxyethylene is not particularly limited, but is preferably 1 thousand (1000) or more and 600 ten thousand (6000000) or less, and more preferably 1 ten thousand (10000) or more and 550 ten thousand (5500000) or less. When the weight average molecular weight is in the above range, the viscosity of the treatment liquid is likely to increase, and the molecular chains are likely to be entangled with the fibers of the fabric. The weight average molecular weight of a water-soluble resin such as polyoxyethylene can be measured by a known method such as a GFC (Gel Filtration Chromatography) method or a GPC (Gel Permeation Chromatography) method.

As the carboxymethyl cellulose, commercially available products can be used, and examples thereof include CMC Daicel (registered trademark) 1120, 1130, 1220, 1240, 1250, and 1330 (trade names shown above, manufactured by Daicel Fine Chem); sodium salts of carboxymethyl cellulose such as Cellogen (registered trademark) 5A, 6A, 7A, PL-15, F-5A, F-7A, F-907A, F-815A, PR-S (above, trade name, first industrial pharmaceutical).

Examples of hydroxyethyl cellulose include commercially available products such as HEC Daicel (registered trademark) SP200, SP400, SP500, SP600, SP850, SP900, SE400, SE550, SE600, SE850, SE900, and EE820 (trade name, Daicel Fine Chem Co., Ltd.); AL-15, AG-15F, AH-15F, AV-15F, AW-15F, AX-15, SW-25F, SZ-25F, CF-G, CF-V, CF-W, CF-X, CF-Y (trade name, Sumitomo Seiko Co., Ltd.) and the like.

As the polyvinylpyrrolidone, commercially available products can be used, and examples thereof include commercially available reagents; polyvinylpyrrolidone K-30, K-30W (trade name, Japan catalyst Co., Ltd.); pitzcol (registered trademark) K-17L, K-30, K-30L, K-30AL, K-60L, K-30, K-50, and K-90; creejus (registered trademark) K-30; aiphtact (registered trademark) K-30PH (trade name, first Industrial pharmaceutical Co., Ltd.) and PVP K-30, PVP K-25, PVP K-17 (trade name, Himalan Co., Ltd.) and the like. The polyvinylpyrrolidone is not limited to a homopolymer, and a copolymer of vinylpyrrolidone and another monomer can be used.

The glass transition temperature of the water-soluble resin is not particularly limited, but is preferably-80 ℃ or higher and 0 ℃ or lower, and more preferably-80 ℃ or higher and-10 ℃ or lower. When the glass transition temperature of the water-soluble resin is in the above range, the frictional fastness and the like can be improved while maintaining the texture of the fabric in the printed and dyed material.

As the other water-soluble resin, for example, hydroxypropylmethylcellulose, cellulose acetate, polyvinyl alcohol, or the like can be used.

The content of the water-soluble resin is preferably 0.3% by mass or more and 7.0% by mass or less, more preferably 0.5% by mass or more and 6.0% by mass or less, and even more preferably 0.6% by mass or more and 5.0% by mass or less, based on the total amount of the treatment liquid composition. When the content is within the above range, the filling effect as the treatment liquid composition can be exhibited in the fabric, and the color developability of the pigment can be further improved. This effect can be more preferably obtained for a polyester fabric having a relatively large mesh size. In addition, the fabric to which the treatment liquid composition is applied can be prevented from being hardened, and the hand can be maintained.

The treatment liquid composition according to the present embodiment contains 0.6 to 5.0 mass% of a water-soluble resin having a molecular weight of 2.8 to 280 ten thousand with respect to the total amount of the treatment liquid composition. With such a configuration, the water-soluble resin is easily dissolved in the ink composition on the fabric, and the viscosity of the ink composition is appropriately increased. The viscosity increases to lower the fluidity of the ink composition, so that the ink composition is less likely to sink into the fabric and easily stays on the surface of the fabric. As a result, the ink composition can be developed satisfactorily.

The molecular weight of the water-soluble resin is preferably 3.0 to 270 ten thousand, more preferably 3.2 to 260 ten thousand. Preferably, the molecular weight range is not less than the lower limit, whereby the effect of appropriately increasing the viscosity of the ink composition adhering to the fabric can be obtained, and good color developability can be obtained. Preferably, when the molecular weight range is not more than the upper limit, the viscosity of the treatment liquid composition becomes appropriate, and the trace of the treatment liquid composition is less likely to remain at the site where the treatment liquid composition is attached. Here, the trace residue means that a difference in appearance such as a change in color tone occurs as a coating trace residue when a part to which the treatment liquid composition is applied is compared with a part to which the treatment liquid composition is not applied.

The treatment liquid composition according to the present embodiment preferably contains a water-soluble resin having a molecular weight of 1000(1 thousand) to 2.5 ten thousand (2 thousand 5 thousand). By containing such a water-soluble resin, the color developability becomes better. Since such a water-soluble resin has a smaller molecular weight than the above-mentioned water-soluble resin having a molecular weight of 2.8 ten thousand (2 ten thousand 8 thousand) to 280 ten thousand, the effect of increasing the viscosity of the ink composition is low, but the water-soluble resin is more rapidly dissolved in the ink composition, and the effect of increasing the viscosity immediately after the adhesion of the ink composition can be obtained. Therefore, by using a water-soluble resin having a molecular weight of 1000 to 2.5 ten thousand and a water-soluble resin having a molecular weight of 2.8 to 280 ten thousand in combination, the color developability can be made more favorable. When the water-soluble resin having a molecular weight of 1000 to 2.5 ten thousand is contained, it is contained preferably in an amount of 0.1 to 5.0% by mass, more preferably in an amount of 0.2 to 4.0% by mass, and further preferably in an amount of 0.5 to 2.0% by mass, relative to the total amount of the treatment liquid composition.

In the present specification, the molecular weight of the water-soluble resin is a molecular weight measured by the above-described GPC method, and is a molecular weight with respect to a standard substance. The measurement of the molecular weight may be performed using a water-soluble resin monomer, or may be performed on a substance as a treatment liquid composition. In this case, it is preferable that the components contained in the treatment liquid composition are clear.

In the present specification, "water-soluble" refers to the above-mentioned characteristics, and "water-soluble component" refers to a component having water solubility among components contained in the treatment liquid composition. More specifically, the water-soluble resin is not limited to the above, but includes a substance having water solubility in a cationic compound.

Water (W)

The treatment liquid composition according to the present embodiment uses water as a main solvent. The water is a component that is evaporated by drying after the treatment liquid is attached to a substrate such as a fabric. As the water, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water, and water such as ultrapure water from which ionic impurities are removed as much as possible can be used. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, the generation of mold or bacteria can be suppressed when the treatment liquid is stored for a long period of time. The main solvent of the treatment liquid composition is not limited to water, and for example, a water-soluble organic solvent may be used as the main solvent.

The content of water contained in the treatment liquid composition may be, for example, 50 mass% or more, preferably 60 mass% or more and 99 mass% or less, more preferably 70 mass% or more and 98 mass% or less, and further preferably 80 mass% or more and 95 mass% or less, with respect to the total amount (100 mass%) of the treatment liquid composition. When the water content is in the above range, the increase in viscosity of the treatment liquid composition can be suppressed, and the workability when the treatment liquid composition is attached to a fabric and the drying property after attachment can be improved. The water in the treatment liquid also includes water used as a raw material of the treatment liquid, for example, water mixed in a resin emulsion or the like described later.

Water-proofing agent

The treatment liquid composition according to the present embodiment preferably contains a water repellent. In the present specification, the water repellent refers to an additive used for the purpose of imparting water repellency to the surface of the fabric to which the treatment liquid composition is applied. When the treatment liquid composition contains a water repellent, since the water repellent can be provided to the surface of the attached fabric, the ink composition containing water as a main medium can be easily left on the surface of the fabric, and the color developability can be improved. In particular, by using the water-soluble resin in combination with the above-mentioned water-soluble resin, the ink composition can be left on the surface of the fabric even immediately after the adhesion of the ink composition until the filling effect by thickening of the water-soluble resin is expressed, and thus the color developability can be further improved.

The water repellent is a compound having a hydrophilic portion and a hydrophobic portion, and may have a particle form, and by using such a water repellent, the water repellent is selectively oriented on the surface of the coating film, and various functions such as water repellency and slidability are expressed. Such a water repellent is not particularly limited, and examples thereof include calcium stearate, ammonium stearate, silicone water repellent, fluorine water repellent, polyethylene wax, paraffin wax, carnauba wax, and polyethylene-paraffin wax. These water-proofing agents may be used singly or in combination of two or more.

Among the above-mentioned water repellent agents, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the water repellent agent is preferably at least one selected from the group consisting of fluorine-based water repellent agents, silicone-based water repellent agents, and paraffin-based resins. The water repellent may be in the form of an oxide or a derivative thereof having a functional group such as a carboxyl group introduced therein. In addition, the water repellent is preferably in the form of resin particles (emulsion) from the viewpoint of further reducing the viscosity. The type of the emulsion includes emulsion polymerization type, forced emulsion type, and self-emulsion type. When the water repellent is resin particles, the film forming property is good due to a decrease in viscosity or the like, and the uniformity in the adhesion surface is good even when the water repellent is added to the treatment liquid composition at a low concentration. In addition, dissolution into the ink composition does not easily occur, and good water resistance is easily obtained.

In the present embodiment, the water repellent is preferably a resin having a melting point of 150 ℃ or lower, more preferably 100 ℃ or lower, and further preferably 70 to 100 ℃. When the melting point is 150 ℃ or lower, the film forming property when the treatment liquid composition is adhered to a fabric is good, and the uniformity in the adhered surface is good even when a water repellent is added to the treatment liquid composition at a low concentration. Further, by setting the melting point to 70 ℃ or higher, the ink composition is less likely to be dissolved, and good water resistance is easily obtained.

As such a water repellent, commercially available products such as AQUACER (registered trademark) 497, 537, 539 (trade name, product of Pickery chemical Co., Ltd., paraffin wax); SF Coat (registered trademark) SWK-601 (trade name, fluorine-based water repellent available from AGC Seimichemical Co., Ltd.).

In the present embodiment, the content of the water repellent is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 0.30% by mass, and further preferably 0.05 to 0.10% by mass in terms of solid content, relative to the total amount of the treatment liquid composition. The color developability of the ink composition can be further improved by setting the content of the water repellent to 0.01 mass% or more; when the content of the water repellent is 5% by mass or less, the graininess of the image can be further reduced and the color unevenness can be reduced.

Resin particle

The treatment liquid composition according to the present embodiment preferably contains resin particles. In the present specification, the resin particles are preferably resin particles different from the water repellent, and as a material for forming the resin particles, polyurethane-based resins, vinyl acetate-based resins, acrylic resins, styrene-acrylic resins, and polyester-based resins are preferable, and at least one of them is preferably used. By using the resin particles, the fixability of the color material (pigment) contained in the ink composition to the fabric can be further improved. In addition, the resin particles may be used as a filler for suppressing excessive penetration (sinking) of the treatment liquid composition or the ink composition into the fabric.

As described in the present embodiment, when the treatment liquid composition contains water as a main solvent, the resin particles can be used as a resin emulsion dispersed in an aqueous medium. As a method for dispersing the resin particles, a forced emulsification type using an emulsifier (surfactant); a self-emulsifying type in which a hydrophilic portion (hydrophilic group) is introduced into the molecular structure of the resin particle, and the like. The resin particles may have reactivity (crosslinking reactivity), and for example, resin particles having an isocyanate group masked by a blocking agent in the molecular structure may be used.

The average particle diameter of the resin particles is preferably 30nm or more and 300nm or less, and more preferably 40n m or more and 100nm or less. When the average particle diameter is within the above range, the dispersibility of the resin emulsion in the treatment liquid composition and the fixability to the fabric can be improved. Here, in the present specification, unless otherwise specified, "average particle diameter" means a volume-standard particle size distribution (50%). The average particle diameter is measured by a dynamic light scattering method or a laser diffraction light method described in JIS Z8825. Specifically, a particle size distribution meter using a dynamic light scattering method as a measurement principle (for example, "microtrack upa", japanese machine).

Commercially available products of this resin emulsion can be used. Examples of the polyurethane resin emulsion include Superflex (registered trademark) 150, 420, 460, 470, 500, 610, 700, 800, 870, 6E-2000, E-2500, E-4000, and R-5000 (the same applies to the first Industrial pharmaceutical Co., Ltd.); a deka Bontighter (registered trademark) HUX-290K, 380, 822 and 830 (trade name, Adeka Corp., supra); takelac (registered trademark) W-6020, 6021, 6061, 605, 635, WS-6021 (trade name, Mitsui chemical polyurethane Co., Ltd., supra); permarin (registered trademark) UA-150 (trade name, Sanyo chemical industries Co., Ltd.); sun Cure (registered trademark) 2710 (trade name, luoborun, japan); NeoRez (registered trademark) R-940, 9637, 9660 (trade name, Nanba cost chemical Co., Ltd.) and the like.

Examples of the vinyl acetate resin emulsion include Vinyblan (registered trademark) 1245L (trade name, japan chemical industry corporation); polysol (registered trademark) SH-502, AD-2, 10, 13, 17, 70, 96 (trade name, Showa Denko K.K.); seikadyne (registered trademark) 1900W (trade name, Dari Seikagan Co., Ltd.), and the like.

Examples of the acrylic resin emulsion include Voncoat (registered trademark) AN-402, R-3110, R-3360 and 4001 (trade name, DIC corporation); polysol (registered trademark) AM-710, 920, 2300, AP-4735, AT-860, PSASE-4210E (trade name, Showa Denko K.K.); saibinol (registered trademark) SK-200(SAIDEN chemical Co.); AE-120A (trade name, JSR Corp.); vinyblan (registered trademark) 2650, 2680, 2682, 2684, 2886, 5202, (trade name, japanese chemical industry corporation); NK-Binder-R-5HN (trade name, Ningzhongcun chemical industries, Ltd.), and the like.

Examples of the styrene-acrylic resin emulsion include Microgel (registered trademark) E-1002, 5002 (trade name, japan lacquer corporation); voncoat (registered trademark) 5454 (trade name, DIC corporation); polysol (registered trademark) AP-7020 (trade name, showa electric corporation, supra); SAE1014 (trade name, Zeon corporation, japan); AE373D (trade name, E-Tech corporation); joncryl (registered trademark) 390, 450, 511, 631, 632, 711, 734, 741, 775, 780, 790, 840, 852, 1535, 7001, 7100, 7600, 7610, 7640, 7641, 74J, 352D, 352J, 537J, 538J, HRC-1645J, PDX-7145, 7630A (above, trade name, BASF corporation); mowinyl (registered trademark) 966A, 7320 (japan synthetic chemical company), and the like.

Examples of the polyester resin emulsion include: eritel (registered trademark) KA-5071S, KT-8701, 8803, 8904, 9204, 0507 (trade name, Unitika Co., Ltd., supra), Hight ch SN-2002 (trade name, Toho chemical Co., Ltd.), and the like.

Among the above resin emulsions, nonionic or cationic resin emulsions are more preferably used in order to suppress the reaction with the cationic polymer.

The content of the resin particles (content in terms of solid content of the resin emulsion) in the treatment liquid composition is preferably 0.1% by mass or more and 20.0% by mass or less, more preferably 0.1% by mass or more and 7.0% by mass or less, and still more preferably 0.5% by mass or more and 1.0% by mass or less, relative to the total amount of the treatment liquid composition. When the content of the resin emulsion in terms of solid content is in the above range, the reduction in storage stability and the increase in viscosity of the treatment liquid composition can be suppressed, and the wash fastness, the friction fastness, and the like in a printed matter can be improved.

Surface active agent

The treatment liquid composition may further contain a surfactant. The surfactant has a function of reducing the surface tension of the treatment liquid composition and improving the permeability to the fabric. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant, and at least one of them can be used. In particular, a nonionic surfactant is preferably used from the viewpoint that the action of the cationic compound is hardly inhibited.

The content of the surfactant added to the treatment liquid composition is preferably 2.0% by mass or less with respect to the total amount of the treatment liquid composition. More preferably 1.5% by mass or less, and still more preferably 1.1% by mass or less. When the content of the surfactant is in the above range, excessive reduction in the surface tension of the treatment liquid composition can be suppressed, and the treatment liquid composition is likely to remain on the surface of the fabric when the treatment liquid composition is adhered. This makes it possible to easily express the function of the treatment liquid composition. The lower limit of the content of the surfactant when added is preferably 0.01% by mass or more based on the total amount of the treatment liquid composition. More preferably 0.05% by mass or more, and still more preferably 0.07% by mass or more. When the content of the surfactant is in the above range, the wettability to the fabric can be improved when the treatment liquid composition is applied.

As the fluorine-based surfactant, commercially available ones can be used, and examples thereof include: such as Megaface (registered trademark) F-479 (trade name, DIC corporation); BYK-340 (trade name, BYK Corp.), and the like.

The silicone surfactant is not particularly limited, and a silicone compound can be used. The polysiloxane compound is not particularly limited, and examples thereof include polyether-modified organosiloxanes. Commercially available products of polyether-modified organosiloxane include: for example, BYK-302, 306, 307, 333, 341, 345, 346, 347, 348 (trade name, BYK Co., Ltd., supra), KF-351A, 352A, 353, 354L, 355A, 615A, 945, 640, 642, 643, 6020, 6011, 6012, 6015, 6017, X-22-4515 (trade name, shin-Etsu chemical industries, supra.), and the like.

Examples of the anionic surfactant include higher fatty acid salts, soaps, α -sulfo fatty acid methyl ester salts, alkylbenzenesulfonates, alkylsulfuric ester salts, alkyl ether sulfuric ester salts, monoalkyl phosphoric ester salts, α -olefin sulfonates, alkylnaphthalene sulfonates, naphthalene sulfonates, alkane sulfonates, polyoxyethylene alkyl ether sulfuric ester salts, sulfosuccinic ester salts, polyoxyalkylene glycol alkyl ether phosphoric ester salts, and the like.

Examples of the cationic surfactant include: for example, quaternary ammonium salt compounds such as alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts, and amine salt compounds such as N-methyldihydroxyethylamine fatty acid ester hydrochloride. The cationic surfactant may be the above cationic compound.

The amphoteric surfactant is not particularly limited, but examples thereof include amino acid compounds such as alkyl amino fatty acid salts.

The nonionic surfactant preferably contains a polyoxyalkylene compound having a structure represented by the following formula (1).

R ⁴-O-X-H……(1)

(in the formula (1), R ⁴Represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, and X represents a polyoxyethylene skeleton or a polyoxypropylene skeleton. )

Further, among the compounds having a structure represented by the above formula (1), a compound having a structure represented by the following formula (1-1) is preferable.

R ⁴-O-(CHR ⁵-CHR ⁶-O) _m-H……(1-1)

(in the formula (1-1), R ⁴Represents a substituted or unsubstituted hydrocarbon group having 16 or more carbon atoms, R ⁵And R ⁶Each independently represents hydrogen or methyl, R ⁵And R ⁶One of them is hydrogen, and m represents an integer of 2 to 20. )

In general formula (1-1)In the nonionic compound represented by (a), one end of a condensed chain of ethylene oxide or propylene oxide is a monoalkyl ether, and the other end is a hydroxyl group. The anionic compound has a condensed chain portion mainly having hydrophilic property, and an alkyl group (R) of an alkylether portion ⁴) Mainly exhibiting hydrophobic properties. Thereby being able to exhibit activity as an emulsifier. In the compound represented by the formula (1-1), when R is ⁴Having 16 or more carbon atoms, it has sufficient hydrophobicity, and thus it is considered to be useful as an emulsifier. In addition, R is more preferable ⁴Has 18 or more carbon atoms. The upper limit of the number of carbon atoms is preferably 20 or less.

By using such a compound, problems of image quality such as graininess and generation of wrinkles of an image can be improved well. This is presumably because the compound represented by the formula (1) can stabilize the dispersion system in the ink and can appropriately suppress the reactivity with the cationic compound. For example, in a pigment printing ink, a resin or the like of a dispersion system in the ink reacts with a cationic compound to aggregate to obtain good color developability and rub fastness, but if the reaction is too fast, dots aggregate before wet spreading, which may cause grainy feel of an image or generation of wind marks. Also, this tendency is more noticeable when ink is attached at a low duty ratio. Further, when the viscosity of the treatment liquid composition is high, or when the water repellency of the treatment liquid composition is too high, wet spreadability may be lowered, and the image may more easily generate a grainy feel, but it is presumed that by containing the compound represented by formula (1), the reaction between the dispersion in the ink and the cationic compound is appropriately suppressed, and by sufficiently wetting the spread, the generation of the grainy feel and the wind marks of the image can be appropriately suppressed.

Examples of the compound having a structure represented by formula (1) include: polyoxyethylene stearic acid ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether. Examples of commercially available products suitable for this include: emulgen 350, Emulgen420 (manufactured by Kao corporation); newcol1860, Newcol1210, Newcol1204 (manufactured by Nippon emulsifier Co., Ltd.). Among them, polyoxyethylene oleyl ether is preferably used as the nonionic surfactant.

In addition, with respect to the nonionic compound represented by the formula (1), an HLB (hydrophilic lipophilic balance) value may be defined, and when the nonionic compound represented by the formula (1) is used, the HLB value is preferably 12 or more, more preferably 13 or more, and further preferably 15 or more. Here, the HLB value is an HLB value defined by Griffin method (Griffin). Such compounds may be exemplified by: e mulgen 350 (polyoxyethylene stearyl ether, R in formula (1)) ⁴Has a carbon number of 18 and an HLB value of 17.8), Emulgen420 (polyoxyethylene oleyl ether, R in formula (1) ⁴Has a carbon number of 18 and an HLB value of 13.6) and Newcol1860 (polyoxyethylene stearyl ether, R of formula (1) ⁴Has a carbon number of 18, an HLB value of 18.1), Newcol1210 (polyoxyethylene oleyl ether, R of formula (1) ⁴C18, HLB value 12.4), Newcol1204 (polyoxyethylene oleyl ether, R of formula (1) ⁴Carbon number of 18, HLB value of 7.9).

As the other nonionic surfactant, an acetylene glycol surfactant, a fluorine surfactant, a silicone surfactant, and the like can be used.

The acetylene glycol surfactant is not particularly limited, and examples thereof include: for example, alkylene oxide adducts such as 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, alkylene oxide adduct of 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, 2, 4-dimethyl-5-decyne-4-ol, alkylene oxide adduct of 2, 4-dimethyl-5-decyne-4-ol, 3, 6-dimethyl-4-octyne-3, 6-diol, 3, 5-dimethyl-1-hexyn-3-ol, 2, 4-dimethyl-5-hexyn-3-ol, and the like.

Commercially available acetylene glycol surfactants can be used. For example, Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (trade name, Air Products and chemicals, inc.); olfine (registered trademark) 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 (above, trade name, japanese chemical industry); acetylenol (registered trademark) E00, E00P, E40, E100 (trade name, Chuanjian Fine chemical Co., Ltd.) and the like.

The above surfactants may be used alone or in combination of two or more. In addition, it is preferable to use a surfactant having an HLB (hydrophilic lipophilic balance) value of 13 or more. Thereby, the penetration into the fabric and wet spreading can be regulated when the treatment liquid composition is applied.

The surfactant used is preferably a nonionic surfactant. The nonionic property does not inhibit the action of the cationic compound.

Other ingredients

Various additives or organic solvents, such as pH adjusters, preservatives, mildewcides, antioxidants, chelating agents, and the like, may be added to the treatment liquid composition.

The pH adjuster is not particularly limited, and examples thereof include organic bases and inorganic bases. Examples of the organic base include: for example, alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, and triisopropanolamine. As the inorganic base, a strong base such as a hydroxide of an alkali metal or an alkaline earth metal, for example, lithium hydroxide, potassium hydroxide, or calcium hydroxide can be used.

Examples of the preservative or the mildewcide include: for example, sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1, 2-dibenzothiazolin-3-one (trade name PROXEL CRL, PROXEL BDN, PROXEL GXL, PR OXEL XL-2, PROXEL TN from LON ZA). By adding a preservative or a mildewproofing agent to the treatment liquid composition, the propagation of bacteria or molds in the treatment liquid composition can be suppressed.

The organic solvent may be added to adjust the physical properties of the treatment liquid such as viscosity and surface tension, the drying property of the treatment liquid composition, and the like. When an organic solvent is added, an organic solvent used in an ink composition described later can be applied.

Method for preparing treatment liquid composition

The treatment liquid composition can be prepared by mixing the above components in an arbitrary order and, if necessary, performing filtration or the like to remove impurities, foreign substances, or the like. As a method for mixing the respective components, a method of sequentially adding the materials (components) to a vessel equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, and stirring and mixing the materials (components) can be adopted. As a filtration method, centrifugal filtration, filter filtration, or the like can be employed.

Physical Properties of treatment liquid composition

The physical properties of the treatment liquid composition can be optionally adjusted depending on the type of fabric, the method of adhering to the fabric (coating method), and the like. The method of applying the treatment liquid composition will be described later.

The viscosity of the treatment liquid at 20 ℃ is not particularly limited, but is preferably 0.5 to 100 mPas (millipascal seconds), more preferably 1 to 50 mPas, and still more preferably 1.5 to 30 mPas. By setting the viscosity of the treatment liquid composition in the above range, the coatability such as easy spreadability of the treatment liquid when it is attached to a fabric can be improved.

When the ink jet method is used as the coating method, the viscosity of the treatment liquid at 20 ℃ is preferably 0.5 to 15mPa · s, more preferably 1 to 5mPa · s, and still more preferably 1.5 to 3.6mPa · s. By setting the viscosity in the case of using the ink jet method to the above range, the stability of the treatment liquid discharged from the ink jet head can be improved, and the treatment time of the step of adhering the treatment liquid can be shortened.

The viscosity of the treatment liquid composition is measured, for example, using a viscoelasticity tester MCR-301 (manufactured by Anton Paar). Specifically, the shear rate can be adjusted from 0.01s to 20 ℃ by adjusting the temperature of the treatment liquid ^-1Increased to 1.00s ^-1Read shear rate of 0.10s ^-1The viscosity of the water was measured.

The surface tension of the treatment liquid composition at 25 ℃ is, for example, preferably 30mN/m or more and 60mN/m or less, and more preferably 35mN/m or more and 50mN/m or less. When the surface tension of the treatment liquid composition at 25 ℃ is in the above range, the treatment liquid composition can be easily left on the surface of the fabric while improving wettability to the fabric when the treatment liquid composition is applied.

The surface tension of the treatment liquid is measured, for example, using an automatic surface tensiometer CBVP-Z (Kyowa interface science Co.). Specifically, the measurement can be performed by reading the surface tension when the platinum gold plate is wetted with the treatment liquid in an environment of 25 ℃.

Molecular weight distribution of water-soluble ingredients

In the treatment liquid composition of the present embodiment, the molecular weight distribution of the water-soluble component contained in the treatment liquid composition has a maximum value in a range of 2.8 ten thousand (2 ten thousand 8 thousand) to 280 ten thousand. Accordingly, the water-soluble component is easily dissolved in the ink composition on the fabric, and the viscosity of the ink composition is preferably increased. The increase in viscosity reduces the fluidity of the ink composition, and the ink composition hardly sinks into the fabric and easily stays on the surface of the fabric. As a result, good color development can be obtained by the ink composition.

The molecular weight distribution of the water-soluble component preferably has a maximum value in a range of 3.0 to 270 ten thousand, and more preferably has a maximum value in a range of 3.2 to 260 ten thousand. When the amount is not less than the lower limit, the effect of appropriately increasing the viscosity of the ink composition can be obtained, and good color developability can be obtained, which is preferable. When the amount is equal to or less than the upper limit, the viscosity of the treatment liquid composition becomes appropriate, and a coating mark of the treatment liquid composition is less likely to occur at a place where the treatment liquid composition is adhered, and therefore, this is preferable.

The treatment liquid composition of the present embodiment further preferably contains a water-soluble component having a molecular weight distribution having a maximum value in the range of 1000 to 2.5 ten thousand, and the ratio of the peak area having a molecular weight of 2.8 to 280 ten thousand to the peak area having a molecular weight of 1000 to 2.5 ten thousand is 1:5 to 5: 1. Thereby, the color rendering property will become better. Since the ink composition has a peak in a region having a molecular weight smaller than that of the molecular weight distribution (2.8 to 280 ten thousand), the ink composition has a low viscosity-increasing effect, but can be dissolved in the ink composition more rapidly, and the viscosity-increasing effect is obtained immediately after the ink composition is attached. Therefore, the color rendering properties can be improved.

In addition, by making the ratio of the peak area having a molecular weight of 2.8 to 280 ten thousand to the peak area having a molecular weight of 1000 to 2.5 ten thousand from 1:5 to 5:1, the viscosity of the treatment liquid composition becomes appropriate. In addition, the dissolution rate into the ink composition and the viscosity after dissolution become appropriate, and good color developability can be obtained. The molecular weight distribution preferably has a maximum in the range of 1200 to 2.2 ten thousand, more preferably in the range of 1500 to 2.1 ten thousand. In addition, the ratio of the peak area having a molecular weight of 2.8 to 280 ten thousand to the peak area having a molecular weight of 1000 to 2.5 ten thousand is more preferably 1:4 to 4:1, and still more preferably 1:3 to 3: 1.

The presence or absence of a maximum value and a peak area in the molecular weight distribution can be known by the SEC method.

Ink composition

Next, an ink composition for producing a printed material by printing on a fabric to which the treatment liquid composition of the present embodiment is applied will be described. The ink composition according to the present embodiment is preferably an aqueous pigment ink for inkjet printing. The pigment ink is more preferable than the dye ink in that the variety of fabrics to which the ink can be applied is wide. On the other hand, although it may be difficult to obtain color developability by internal penetration of the fabric in the pigment ink, the use of the treatment liquid composition of the present invention can improve color developability. Further, by adopting ink jet printing by an ink jet method as a printing method, it is possible to produce a high-definition image or the like with a reduced production cost as compared with conventional dummy printing.

The ink composition used in the present embodiment is a pigment printing ink jet ink composition (hereinafter simply referred to as "ink composition") containing a pigment, resin particles and water. The ink composition used in the present embodiment may be used together with the treatment liquid composition according to the present embodiment to form an ink jet textile printing composition set.

In addition, a white ink containing a white pigment as a pigment (white pigment printing ink jet ink composition) is preferably contained in the ink jet printing composition set. In addition, in the ink jet textile printing composition set, a color ink containing a color pigment (color pigment printing ink jet ink composition) is preferable in addition to the white ink. In this case, in the ink jet pigment printing method described later, double-layer printing in which color printing is performed on a white background becomes possible. Hereinafter, the components contained in the ink composition of the present embodiment will be described.

Color material

The ink composition of the present embodiment uses a pigment as a coloring material. By using a pigment as the coloring material, the steps such as the dyeing step and the washing step can be simplified as compared with the case of using a dye.

As the pigment, any known organic pigment and inorganic pigment can be used. Examples of the organic pigment include: azo pigments such as azo lake pigments, insoluble azo pigments, condensed azo pigments, and chelate azo pigments; phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, isoindoline pigments, quinophthalone pigments, diketopyrrolopyrrole pigments and other polycyclic pigments, basic dye type lakes, acid dye type lake pigments and other dye lake pigments, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments and the like. Examples of the inorganic pigment include: for example, metal oxide pigments such as titanium dioxide, zinc oxide, and chromium oxide; carbon black, and the like. In addition, bright pigments such as pearl pigments and metallic pigments may be used.

Examples of such pigments include: for example, c.i. (Co lor indexgenic Name) pigment black 1, 7, and 11 are used as black pigment ink. Among them, carbon black (c.i. pigment black 7) having a small specific gravity and hardly sedimenting in an aqueous medium is preferable for ink jet textile printing.

Examples of the color pigment ink (color ink) include: for example, c.i. pigment yellow 1,3, 12, 13, 14, 17, 24, 34, 35, 37, 42, 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 153, 155, 180; c.i. pigment red 1,2, 3,5, 17, 22, 23, 31, 38, 48:2 (permanent red 2b (ba)), 48:2 (permanent red 2b (ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1, 60:1, 63:2, 64:1, 81, 83, 88, 101, 104, 105, 106, 108, 112, 114, 122, 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 219; c.i. pigment violet 19, 23; c.i. pigment blue 1,2, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60, 63; c.i. pigment green 1,4, 7, 8, 10, 17, 18, 36, etc. The average particle diameter of the pigment is preferably 5 μm or less, more preferably 0.3 μm or less, and still more preferably in the range of 0.01 to 0.15. mu.m. By setting the average particle diameter of the pigment in the above range, the stability of the ink composition ejected from the ink jet head can be ensured, and the color developability of the pigment in the printed material can be improved.

The treatment liquid composition of the present embodiment is more preferably used for printing a white ink containing a white pigment in order to improve the color developability of the pigment. Specifically, there is a method of first printing a white ink to form a foundation layer when printing a color image or the like on a colored fabric colored in advance. This is done to suppress the influence of the color (cloth color) of the fabric on the color image to be printed and to improve the color development of the image to be printed. That is, if the treatment liquid composition and the white ink of the present embodiment are used, a foundation layer with enhanced hiding properties can be formed by the color developability of the white pigment, and an image or the like of a desired color tone can be printed regardless of the color of the fabric.

Examples of the white pigment for the white ink include: for example, c.i. pigment white 1 (basic lead carbonate), 4 (zinc oxide), 5 (a mixture of zinc sulfide and barium sulfate), 6 (titanium dioxide), 6: 1 (titanium dioxide containing other metal oxides), 7 (zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (mica titanium), 21 (barium sulfate), 22 (gypsum), 26 (magnesium oxide-silica), 27 (silica), 28 (anhydrous calcium silicate) and the like. Among them, c.i. pigment white 6 excellent in color developability, hiding property, and the like is preferably used.

The average particle diameter of the white pigment is preferably in the range of 100 to 450 μm, more preferably 200 to 400 μm, and still more preferably 250 to 380 μm. When the average particle diameter of the white pigment is in the above range, the ejection stability of the white ink ejected from the inkjet head can be ensured, and the color masking property with respect to the fabric cloth can be improved.

For the measurement of the average particle diameter of the pigment, the same method as that of the above-mentioned resin fine particles can be employed.

The content of the pigment when used is not particularly limited, and is preferably, for example, 0.1 to 50.0 mass% based on the total amount of the pigment ink. More preferably 1.0 to 20.0 mass%, and still more preferably 1.0 to 15.0 mass%. When the content of the pigment is in the above range, the color developability of the pigment can be ensured in a printed material subjected to printing and dyeing, and the increase in viscosity of the ink composition and the occurrence of clogging in the inkjet head can be suppressed.

One of the above pigments may be used alone, or two or more of them may be used in combination. In order to improve dispersibility in the ink composition, it is preferable to perform surface treatment on the pigment, or to blend a dispersant or the like in the ink composition. The surface treatment of the pigment refers to a method of introducing a hydrophilic group such as a carboxyl group or a sulfo group to the particle surface of the pigment by physical treatment or chemical treatment. The pigment can be dispersed in an aqueous medium such as water by surface treatment of the pigment.

The dispersant for an aqueous medium has a function in which a hydrophobic portion (hydrophobic group) in a molecular structure is adsorbed on the particle surface of a pigment, and a hydrophilic portion (hydrophilic group) faces the medium side. By this action, the pigment can be dispersed in an aqueous medium. As the dispersant, a known surfactant or a polymer compound is used. Further, a method of coating the pigment particles with a polymer compound or the like to impart dispersibility may be employed. As a method for covering the pigment particles, an acid precipitation method, a phase inversion emulsification method, a microemulsion polymerization method, or the like can be used.

Water (W)

The ink composition used in the present embodiment is preferably an aqueous ink. When an aqueous ink composition is used, water is the main solvent of the ink composition of the present embodiment. After the ink composition is deposited, water evaporates from the fabric by drying. The same water as the above-mentioned treatment liquid composition can be used as the water. The water content in the ink composition is, for example, 30% by mass or more and 90% by mass or less, preferably 40% by mass or more and 85% by mass or less, and more preferably 50% by mass or more and 80% by mass or less, based on the total amount of the ink composition. When the water content is within the above range, the increase in viscosity of the ink composition can be suppressed. In the present specification, the term "water-based ink" refers to an ink composition in which the content of water is 30% by mass or more relative to the total amount of the ink composition.

Organic solvent

An organic solvent may be added to the ink composition. By adding the organic solvent, physical properties such as viscosity and surface tension, and behaviors such as drying and penetration when attached to a fabric can be adjusted. Examples of the organic solvent include: for example, 2-pyrrolidones, 1, 2-alkanediols, polyols, glycol ethers, and the like. These may be used singly or in combination of two or more.

The 2-pyrrolidones mean compounds having a 2-pyrrolidone skeleton. Examples of the 2-pyrrolidone include compounds having a substituent such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-vinyl-2-pyrrolidone, in addition to 2-pyrrolidone having no substituent. The substituent in the 2-pyrrolidone skeleton is preferably an organic group such as a saturated or unsaturated hydrocarbon group having 1 to 5 carbon atoms. Among them, 2-pyrrolidone, which is excellent in storage stability of the ink composition and an effect of suppressing generation of aggregates, is more preferably used.

Examples of the 1, 2-alkanediol include 1, 2-propanediol, 1, 2-butanediol, 1, 2-pentanediol, 1, 2-hexanediol, and 1, 2-octanediol. The 1, 2-alkanediols are excellent in improving the wettability of the ink composition to a fabric and in a uniform wetting action. Therefore, an image or the like in which the occurrence of bleeding is suppressed can be formed. The content of the 1, 2-alkanediol added is preferably 1 to 20% by mass based on the total amount of the ink composition.

Examples of the polyhydric alcohols include: for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 3-pentanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-2, 4-pentanediol, glycerol and the like. By adding the polyhydric alcohol to the ink composition, drying or curing of the ink composition in the discharge nozzle of the inkjet head can be suppressed, and clogging of the discharge nozzle, discharge failure, or the like can be reduced. The content of the polyol when added is preferably 2 to 20% by mass based on the total amount of the ink composition. In addition, solid polyols at 20 ℃ also have the same action as organic solvent polyols, and can be used in the same way. Examples of the polyhydric alcohol which is solid at 20 ℃ include trimethylolpropane and the like.

Examples of the glycol ethers (glycol ethers) include alkylene glycol monoethers and alkylene glycol diethers.

Examples of the alkylene glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether (butyl triethylene glycol), tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

Examples of the alkylene glycol diether include: for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and the like.

By adding the glycol ether to the ink composition, the wettability to a fabric (for example, a polyester fabric) and the permeation rate can be adjusted. The content of the glycol ether when added is preferably 0.05 mass% or more and 6 mass% or less with respect to the total amount of the ink composition.

The organic solvent may be used in combination of a plurality of kinds. In this case, the total content of the organic solvents in the ink composition is 0.2% by mass or more and 30% 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, based on the total amount of the ink composition. When the total content of the organic solvent is in the above range, the increase in viscosity of the ink composition can be suppressed, and the behavior (penetration and wet spreading) of the fabric can be adjusted, whereby ejection failure of the inkjet head and the like can be reduced.

Surface active agent

A surfactant may be added to the ink composition. The surfactant has a function of reducing the surface tension of the ink composition and improving the permeability into the polyester fabric. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant, and at least one of them can be used. These surfactants can be the same surfactants as those used in the above-mentioned treatment liquid composition.

The content of the surfactant in the ink composition is 0.01 to 3.00 mass% based on the total amount of the ink composition. Preferably 0.05 to 2.00 mass%, more preferably 0.10 to 1.00 mass%, and still more preferably 0.20 to 0.50 mass%. When the content of the surfactant is within the above range, foaming can be suppressed, stability of ejection from the inkjet head can be ensured, and functions such as aggregation of the treatment liquid composition can be promoted by easily contacting with components of the treatment liquid composition adhering to the fabric.

Chelating agents

A chelating agent may be added to the ink composition. The chelating agent has a function of capturing metal ions and the like. Therefore, when the chelating agent is used in the ink composition, the generation of foreign matter derived from metal ions can be reduced by capturing metal ions contained as impurities in the ink composition or metal ions mixed from a member with which the ink composition is in contact. Examples of the chelating agent include: for example, Ethylenediaminetetraacetate (EDTA), nitrilotriacetate, hexametaphosphate, pyrophosphate, metaphosphate, and the like.

pH regulator

A pH adjuster may be added to the ink composition. The pH adjuster is not particularly limited, and examples thereof include organic bases and inorganic bases. It is preferable to use these pH regulators to adjust the pH of the ink composition to a range of 7.5 to 10.5. By setting the pH of the ink composition to the above range, corrosion of materials such as an ink repellent film can be suppressed in an ink jet textile printing apparatus including an ink jet head.

Examples of the organic base include: for example, alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, and triisopropanolamine. Here, in order to make the pH of the ink composition within the above range using these organic bases, a relatively large amount needs to be added. Specifically, the content is, for example, about 0.1 mass% or more and 3 mass% or less with respect to the total amount of the ink composition.

As the inorganic base, for example, a strong base of an alkali metal or alkaline earth metal hydroxide such as lithium hydroxide, potassium hydroxide, or calcium hydroxide can be used. In order to adjust the pH of the ink composition to the above range using these inorganic bases, the content may be, for example, about 0.03 mass% or more and 0.15 mass% or less with respect to the total amount of the ink composition. Thus, the amount of the inorganic base to be added is preferably small compared with the organic base, and the inorganic base does not have odor or the like as the organic base.

Resin particle

The ink composition preferably contains resin particles. By containing the resin particles, the washing fastness and rubbing fastness of the printed matter are further improved. The resin particles may be the same resin emulsion as the treatment liquid composition.

The content of the resin particles is preferably 2 mass% or more and 40 mass% or less, more preferably 4 mass% or more and 35 mass% or less, and further preferably 5 mass% or more and 33 mass% or less, in terms of solid content, relative to the total amount of the ink composition. When the content ratio of the resin particles is in the above range, the washing fastness and rubbing fastness of the printed matter can be further improved while the occurrence of clogging in the nozzle of the inkjet head is reduced.

Other ingredients

In the ink composition, as other components, various additives such as an antioxidant, a preservative and a fungicide similar to those of the treatment liquid can be suitably used.

Preparation of ink composition

The ink composition according to the present embodiment can be prepared by mixing the above components in an arbitrary order, and if necessary, performing filtration or the like to remove impurities, foreign substances, and the like. As a method for mixing the respective components, a method is employed in which materials (components) are sequentially added to a vessel equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed. The filtration method can employ centrifugal filtration, filter filtration, or the like.

Physical Properties of ink composition

The viscosity of the ink composition is preferably 2 mPas to 15 mPas at 20 ℃. More preferably 2 to 5 mPas, still more preferably 2 to 3.6 mPas. By setting the viscosity of the ink composition within the above range, the ejection stability and ejection amount of the composition from the inkjet head can be ensured. In addition, in the case of a viscosity deviating from the above range, there are cases where the ejection stability of the ink composition can be ensured by changing the ejection condition of the ink composition in the inkjet head and the kind of the inkjet head, for example, under the temperature adjustment condition, there are cases where the ejection stability of up to 22mPa · s can be ensured. The viscosity of the ink composition can be measured by the same method as that for the treatment liquid composition described above.

The surface tension of the ink composition at 25 ℃ is preferably 10mN/m or more and 40mN/m or less, and more preferably 25mN/m or more and 40mN/m or less. When the surface tension of the ink composition at 25 ℃ is in the above range, the wettability to fabric and the contact with the components of the treatment liquid composition can be promoted during printing. The viscosity and surface tension of the ink composition can be measured by the same method as that for the treatment liquid composition.

Printing and dyeing apparatus

Printer with a movable platen

Next, a printing apparatus according to the present embodiment will be described with reference to fig. 1. The textile printing apparatus according to the present embodiment is preferably an inkjet textile printing apparatus. An ink jet textile printing apparatus is an apparatus that performs textile printing by ejecting droplets of an ink composition onto a fabric by an ink jet method that ejects the droplets. Fig. 1 is a schematic perspective view showing an inkjet textile printing apparatus according to an embodiment. In the present embodiment, a shelf printer in which an ink cartridge is mounted on a carriage will be described as an example of an inkjet textile printing apparatus. In fig. 1, the dimensions of the components are different from those of the actual components in order to make the sizes of the components recognizable.

The printer 1 of the present embodiment is a so-called serial printer. The serial printer is a printer in which an ink jet head is mounted on a carriage that moves in a predetermined direction, and the ink jet head moves in accordance with the movement of the carriage to perform printing.

As shown in fig. 1, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The ink cartridges 7a, 7b, 7c, 7d, 7e, 7f for containing the ink composition supplied to the ink-jet head 3 can be attached to the carriage 4 or detached from the carriage 4 while the carriage 4 is loaded with the ink-jet head 3.

The main scanning mechanism 5 includes a timing belt 8 connected to the carriage 4, a motor 9 for driving the timing belt 8, and a guide shaft 10. The guide shaft 10 is a support member for the carriage 4 and extends in the scanning direction (main scanning direction) of the carriage 4. The carriage 4 is driven by a motor 9 via a timing belt 8 and can move back and forth along a guide shaft 10. Thus, the main scanning mechanism 5 has a function of moving the carriage 4 back and forth in the main scanning direction.

The platen roller 6 has a function of conveying the fabric 2 to be subjected to printing in a sub-scanning direction (a longitudinal direction of the fabric 2) perpendicular to the main scanning direction. Accordingly, the fabric 2 is conveyed in the sub-scanning direction. The carriage 4 on which the ink jet head 3 is mounted can move back and forth in the main scanning direction substantially coinciding with the width direction of the fabric 2, and the ink jet head 3 can relatively scan the fabric 2 in the main scanning direction and the sub-scanning direction.

The ink cartridges 7a, 7b, 7c, 7d, 7e, 7f are independent 6 ink cartridges. The ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f can contain the ink composition of the present embodiment. The ink cartridges individually contain ink compositions of colors such as black, cyan, magenta, yellow, white, orange, and the like, and can be used in any combination. In fig. 1, the number of ink cartridges is 6, but is not limited thereto. Supply ports (not shown in the drawings) for supplying the ink compositions contained in the respective ink cartridges to the ink-jet head 3 are provided in the bottom portions of the ink cartridges 7a, 7b, 7c, 7d, 7e, 7 f.

The ink jet head 3 has a nozzle surface (not shown) on a surface facing the fabric 2. On the nozzle surface, nozzle rows (not shown) each including a plurality of nozzles (not shown) are arranged corresponding to the respective color ink compositions. The ink compositions of the respective colors are supplied from the respective ink cartridges to the inkjet head 3, and are ejected as droplets from the nozzles by actuators (not shown in the drawings) in the inkjet head 3. The discharged droplets of the ink composition land on the fabric 2, and an image, characters, a pattern, colors, and the like are formed on the printed region of the fabric 2.

Here, the inkjet head 3 uses a piezoelectric element as an actuator (driving mechanism), but is not limited to this type. For example, an electromechanical conversion element that displaces a vibration plate as an actuator by electrostatic attraction, or an electrothermal conversion element that ejects an ink composition as droplets by bubbles generated by heating may also be used.

In the present embodiment, the on carriage printer 1 is used as an example of the inkjet textile printing apparatus, but the present invention is not limited thereto. For example, an under-carriage (offcarriage) printer may be used in which an ink container such as an ink cartridge is not mounted on a carriage. The ink jet textile printing apparatus used in the present invention is not limited to the above serial printer, and may be a line head printer in which an ink jet head is formed to be wider than or equal to the width of the fabric 2, and textile printing is performed without moving the ink jet head.

Fabric

Examples of the form of the fabric 2 according to the present embodiment include a cloth, a garment, and other clothing items. The cloth includes textile, knitting, non-woven fabric, etc. Clothing and other accessories include furniture such as sewn T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, sheets, bedspreads, wallpaper, and the like, and cloth before and after cutting as a member before sewing. Examples of such forms include a long form wound into a roll, a form cut into a predetermined size, and a form of a product shape.

The fabric 2 is preferably a polyester fabric containing polyester. Since polyester fabric has lower fiber hydrophilicity than cotton, an aqueous pretreatment agent or ink composition is easily repelled by polyester fibers and tends to be more difficult to fix to fibers than cotton fabric. In addition, in order to improve air permeability, the polyester fabric is generally formed with relatively large (thick) stitches, and therefore the ink composition may be more likely to sink into the interior of the fabric. Therefore, it has been difficult to obtain good color developability in a polyester fabric in the past, but according to the treatment liquid composition of the present invention, good color developability can be obtained in a polyester fabric.

The polyester fabric is a fabric comprising a polyester fiber and formed from a polyester fiber monomer or a blend fiber of a polyester fiber and another fiber. Examples of the other fibers include natural fibers such as cotton, silk, hemp, and wool, and synthetic fibers such as polypropylene, acetate, triacetate, polyamide, polyurethane, and polylactic acid. The polyester fabric is preferably a fabric made of a polyester fiber monomer (polyester) or a blend of polyester and cotton.

The fabric 2 has a basis weight of 1.0oz (ounce) to 10.0oz, preferably 2.0oz to 9.0oz, more preferably 3.0oz to 8.0oz, and even more preferably 4.0o z to 7.0 oz. In the treatment liquid of the present embodiment, since the components of the treatment liquid composition such as the cationic compound are held on the surface side with respect to the fabric 2 having the basis weight in the above range, the color developability can be improved as compared with the conventional one. In addition, the fabric can be used for a plurality of kinds of fabrics having different basis weights.

The fabric 2 is preferably a polyester fabric colored in advance with a dye or the like. Since the color developability is improved by the treatment liquid composition of the present embodiment, the color of the raw fabric is masked, and interference with the color of the raw fabric is suppressed. That is, the polyester fabric can be preferably used for a polyester fabric having a colored portion. Further, by using the colored cloth, a printed material (product) that meets the preference of the customer can be provided.

The colored fabric preferably has a L value of the colored portion of 80 or less. Here, the L value can be measured using a known color measuring machine, and can be measured using, for example, Spectrolino (Gretag). In the case of a fabric having an L value of 80 or less, the color of the fabric itself may be visible through the attached portion of the ink composition when the ink composition is attached, and in order to prevent this, a higher color developability (hiding property) is required for the ink composition. In addition, in the case of a polyester fabric, as described above, it has been difficult to obtain good color developability.

In contrast, according to the present invention, since the ink composition can be favorably retained on the surface of the fabric by the treatment liquid composition of the present invention, the color developability becomes good, and the treatment liquid composition can be suitably applied to a fabric having an L value of 80 or more. The value of L may be 75 or less, or 70 or less. The treatment liquid composition of the present invention is also excellent in color developability for such a dark fabric, and can be suitably used.

Examples of the dye to which the fabric 2 is colored in advance include: water-soluble dyes such as acid dyes, basic dyes, and the like; and a disperse dye with a dispersant (surfactant); reactive dyes, and the like. Since the fabric 2 contains polyester fibers, a disperse dye suitable for dyeing polyester fibers is preferably used. As the disperse dye suitable for dyeing polyester fibers, a compound that is difficult to sublime in a heating step described later is preferable. As such a disperse dye, a known disperse dye can be used. Further, the disperse dye is preferably used in combination with a dispersant. As the dispersant, a known dispersant such as a surfactant can be used.

As a method for coloring the fabric 2 with a dye, a known method can be employed depending on the material, form, and the like of the fabric 2.

Ink jet printing method

Next, an ink jet textile printing method according to the present embodiment will be described. The inkjet textile printing method of the present embodiment includes a treatment liquid composition adhesion step of adhering a treatment liquid composition to a fabric. The method further includes an ink composition adhesion step of adhering a pigment printing ink jet ink composition containing a pigment, resin particles, and water to a region where the treatment liquid composition adheres, after the treatment liquid composition adhesion step.

Treatment liquid composition adhesion step

In the treatment liquid composition adhesion step, in order to improve the color development of the pigment in the printed matter, the treatment liquid composition in which the components of the ink composition are aggregated is adhered to the fabric before the ink composition is adhered to the fabric. That is, the fabric 2 is preferably a fabric to which the treatment liquid composition of the present embodiment is applied.

The above treatment liquid composition was used as a treatment liquid composition to be attached to a fabric. The amount of the treatment liquid composition adhered is preferably 0.02g/cm ²Above 0.5g/cm ²Attached in the following manner, more preferably at 0.02g/cm ²Above 0.24g/cm ²The following attachment is made. When the amount of the treatment liquid composition to be applied is in the above range, the treatment liquid composition can be easily and uniformly applied to the fabric, and the occurrence of uneven aggregation of images in the printed material can be suppressed, thereby improving the color development.

In the treatment liquid composition adhesion step, when the treatment liquid composition contains a polyvalent metal salt, the adhesion amount of the polyvalent metal salt contained in the treatment liquid composition adhering to the fabric is preferably 1.6 μmol/cm ²Above 6 mu mol/cm ²Attached in the following manner, more preferably at 2. mu. mol/cm ²Above 5 mu mol/cm ²The following attachment is made. By allowing the polyvalent metal salt to adhere in an amount of 1.6. mu. mol/cm ²The adhesion in the above manner makes the color developability of the image in the printed matter good. Further, the amount of the polyvalent metal salt deposited was adjusted to 6. mu. mol/cm ²The frictional fastness of the image becomes good by adhesion in the following manner.

Examples of the method for adhering the treatment liquid composition to the fabric include: for example, any method can be used, such as a method of immersing a fabric in the treatment liquid composition (dip coating), a method of applying the treatment liquid composition with a roll coater or the like (roll coating), a method of spraying the treatment liquid composition with a spraying device or the like (spray coating), and a method of spraying the treatment liquid composition with an ink jet method (ink jet coating). When the treatment liquid composition adhesion step is performed by inkjet coating, the treatment liquid composition can be more uniformly adhered to the fabric 2, which is preferable. Further, it is preferable to adhere the treatment liquid composition by roll coating or spray coating because the degree of freedom in designing the amount of the treatment liquid composition to be adhered is increased and a trouble at the time of adhesion is less likely to occur.

The ink jet textile printing method according to the present embodiment may further include a drying step of the treatment liquid composition for drying the treatment liquid composition adhered to the fabric after the treatment liquid composition adhering step. The treatment liquid composition may be dried by natural drying, and from the viewpoint of increasing the drying rate, drying with heating is preferred. In the drying step of the treatment liquid composition, when heating is performed, the heating method is not particularly limited, and examples thereof include: such as a hot press method, an atmospheric steam method, a high pressure steam method, and a heat fixing method. The heat source for heating may be, for example, infrared rays (lamp).

The heating temperature in the drying step is not particularly limited, and is, for example, preferably 170 ℃ or lower, more preferably 150 ℃ or lower, and still more preferably 130 ℃ or lower. Thus, even if the fabric is colored with the disperse dye (sublimation dye) in advance, sublimation of the disperse dye by heat drying can be suppressed, and fading of the gray fabric color of the fabric 2 can be suppressed. The lower limit of the heating temperature is not particularly limited as long as the medium such as water contained in the treatment liquid volatilizes, and is preferably 100 ℃ or higher.

The heating temperature is preferably about the same as the heating temperature after the adhesion of the ink composition described later, since the drying process can be simplified. Here, the heating temperature in this step is the surface temperature of the treatment liquid composition adhering to the fabric, and can be measured, for example, by using a non-contact thermometer IT2-80 (trade name, japan chinstian corporation). The heating time for heating is not particularly limited, and is, for example, 30 seconds to 20 minutes.

Ink composition adhesion step

In the ink composition adhesion step, the ink composition used in the present embodiment is adhered to the fabric in the area where the treatment liquid composition is adhered. Here, the ink composition described above is used as the ink composition. Among the ink compositions, a pigment printing ink jet ink composition containing a pigment, resin particles and water is preferable from the viewpoint of preferably exhibiting the effects of the present invention. The ink composition adhesion step may include a step of adhering different ink compositions to the region to which the ink composition adheres. For example, a white ink composition containing a white pigment may be first deposited, and a color ink composition containing a color pigment may be deposited on the region where the white ink composition is deposited. In the case where the ink composition adhesion step has these two steps, double-layer printing is recorded in which an image is formed by a color ink composition on an image formed by a white ink composition. As a method for attaching the ink composition to the fabric, an inkjet method is preferably used.

Since the ink jet textile printing method according to the present embodiment has the treatment liquid composition adhesion step using the treatment liquid composition, permeation of the adhered ink can be appropriately suppressed in the ink composition adhesion step, and the ink can be left on the surface of the fabric. In addition, the ink components aggregate by the reaction or interaction of the cationic compound of the treatment liquid composition with the ink components. Thus, a printed material having excellent color rendering properties is obtained.

In the ink composition deposition step, when the ink composition is a white ink containing a white pigment (white pigment printing ink jet ink composition), the maximum deposition amount to the fabric is preferably 50mg/cm ²Above 200mg/cm ²It is attached to the fabric in the following manner, more preferably 80mg/c m ²Above 150mg/cm ²It is more preferably attached at 90mg/cm in the following manner ²Above 130mg/cm ²The following attachment is made. When the maximum amount of the white ink deposited is as described above, the color developability of white becomes good, and particularly the color developability when the white ink is deposited on a dark fabric is excellent, and the white ink is preferable as a background image. Since a white image with good color development is provided in a color image, when a color image is formed on a dark fabric, the color image is not affected by the color of the fabric, and the color development is good. In addition, if the amount of adhesion is within the above range, the rubbing fastness of the image is excellent and the aggregation unevenness tends not to be conspicuous, which is preferable.

On the other hand, in the ink composition deposition step, in the case where the ink composition is a color ink (color pigment printing ink jet ink composition), the maximum deposition amount onto the fabric may be 1mg/cm ²Above 200mg/cm ²Hereinafter, it is preferably 1mg/cm ²Above 30mg/cm ²Hereinafter, more preferably 2mg/cm ²Above 25mg/cm ²Hereinafter, more preferably 5mg/cm ²Above 20mg/cm ²Below, particularly preferably 7mg/cm ²Above 15mg/cm ²The following. In this case, the recorded image is preferable because the color developability is good, the drying property of the recorded image is good, bleeding of the image can be suppressed, and an image such as a picture or a character can be recorded on a fabric with good reproducibility.

Heating step

The ink jet textile printing method according to the present embodiment preferably includes a step of heating the fabric after the ink composition adhesion step. The heating step facilitates uniform wetting of the ink composition on the fabric, and promotes fixation of the ink composition on the fabric.

The heating method for heating the ink composition applied to the fabric is not particularly limited, and examples thereof include: hot pressing, atmospheric steam, high pressure steam, hot air drying, and heat fixing.

The heating temperature is not limited to this, and is preferably 100 ℃ to 200 ℃ inclusive, and more preferably 100 ℃ to 170 ℃ inclusive. When the fabric is cotton, the temperature is preferably 120 ℃ to 160 ℃, and when the fabric is formed of polyester or polyester blended yarn, the temperature is more preferably 100 ℃ to 150 ℃. When the heating temperature is within the above range, damage to the fabric can be reduced, or film formation of the resin particles contained in the ink composition can be promoted.

The heating time is not limited to this, and may be, for example, 30 seconds to 20 minutes, preferably 2 minutes to 7 minutes, and more preferably 3 minutes to 5 minutes. By setting the heating time within the above range, the ink can be sufficiently dried while reducing damage to the fabric. Further, it is preferable that the heating temperature is about the same as the heating temperature after the treatment liquid composition is adhered, since the drying step can be simplified. The heating temperature in this step is the surface temperature of the treatment liquid composition adhering to the fabric, and can be measured, for example, by a non-contact thermometer I T2-80 (trade name, japan chinst corporation).