US20200040523A1

US20200040523A1 - Treatment Liquid Composition, Set, Ink Jet Printing Method, And Cloth

Info

Publication number: US20200040523A1
Application number: US16/526,190
Authority: US
Inventors: Ryota MIYASA; Masakazu Ohashi
Original assignee: Seiko Epson Corp
Current assignee: Seiko Epson Corp
Priority date: 2018-07-31
Filing date: 2019-07-30
Publication date: 2020-02-06
Also published as: CN110776787B; JP2020019173A; CN110776787A

Abstract

A treatment liquid composition is a treatment liquid composition which is used to be adhered to a cloth and which includes a cationic compound, a water-soluble resin, and water; a molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum peak in a molecular weight range of 28,000 to 2,800,000; and a content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to a total mass of the treatment liquid composition.

Description

The present application is based on, and claims priority from, JP Application Serial Number 2018-143267, filed Jul. 31, 2018, the disclosure of which is hereby incorporated by reference herein in its entirety.

BACKGROUND

1. Technical Field

The present disclosure relates to a treatment liquid composition, a set, an ink jet printing method, and a cloth.

2. Related Art

Heretofore, when a printed material is formed by dyeing a substrate, such as a cloth, with a colorant, in order to improve a chromogenic property of the colorant, a technique in which a pre-treatment is performed on the substrate using a treatment liquid which contains a cationic compound and the like has been known. For example, JP-A-2008-266853 has proposed as the treatment liquid described above, an ink jet-printing pre-treatment agent which contains a water-soluble polyvalent metal salt and a specific resin emulsion.
However, in recent years, a printed material formed by ink jet printing has been required to have a higher chromogenic property, and according to the treatment liquid disclosed in JP-A-2008-266853, a problem in that a sufficient improvement in chromogenic property is not obtained in some cases may arise. In addition, in order to improve the chromogenic property of the colorant of the printed material, when the contents of the water-soluble polyvalent metal salt and the specific resin emulsion in the treatment liquid are increased, the viscosity of the treatment liquid composition is disadvantageously liable to be increased.

SUMMARY

According to several aspects of the present disclosure, since the problems described above are overcome, a treatment liquid composition having a preferable viscosity, a set, an ink jet printing method, and a cloth, each of which can obtain a printed material having an excellent chromogenic property, are provided.
A treatment liquid composition of the present disclosure is a treatment liquid composition which is used to be adhered to a cloth and which comprises a cationic compound, a water-soluble resin, and water; a molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum peak in a molecular weight range of 28,000 to 2,800,000; and a content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to a total mass of the treatment liquid composition.
According to the treatment liquid composition described above, the molecular weight distribution of the water-soluble component may further have a maximum peak in a molecular weight range of 1,000 to 25,000, and the ratio of a peak area of a molecular weight of 28,000 to 2,800,000 to a peak area of a molecular weight of 1,000 to 25,000 may be 1:5 to 5:1.
According to the treatment liquid composition described above, the water-soluble resin may be at least one selected from a poly(ethylene oxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and a poly(vinyl pyrrolidone).
The treatment liquid composition described above may further comprise a water repellant, and the content of the water repellant may be 0.01 to 0.30 percent by mass with respect to the total mass of the treatment liquid composition.
According to the treatment liquid composition described above, the water repellant may be at least one selected from a fluorine-based water repellant, a silicone-based water repellant, and a paraffin wax.
According to the treatment liquid composition described above, the water repellant may be a resin having a melting point of 100° C. or less.
According to the treatment liquid composition described above, the cloth may be a polyester or a blend containing a polyester and a cotton.
According to the treatment liquid composition described above, the cloth is a cloth having a color portion, and an L* value of the color portion may be 80 or less.
The treatment liquid composition described above may further comprise resin particles.
The treatment liquid composition described above may further comprise a nonionic surfactant, and the nonionic surfactant may be a polyoxyethylene oleyl ether.
According to the treatment liquid composition described above, the cationic compound may be a polyvalent metal salt, and the polyvalent metal salt may be at least one selected from calcium nitrate, calcium chloride, and magnesium sulfate.
The treatment liquid composition described above may be used for ink jet pigment printing.
A set according to the present disclosure comprises: the treatment liquid composition described above; and a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water.
According to the set described above, the pigment-printing ink jet ink composition may be a white ink containing a white pigment.
An ink jet printing method according to the present disclosure comprises: a treatment liquid composition adhesion step of adhering the treatment liquid composition described above to the cloth.
The ink jet printing method described above may further comprise: after the treatment liquid composition adhesion step is performed, an ink composition adhesion step of adhering a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water to a region to which the treatment liquid composition is adhered.
A cloth according to the present disclosure is a cloth to which the treatment liquid composition described above is adhered.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGURE is a schematic perspective view showing an ink jet printing apparatus according to an embodiment.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Hereinafter, embodiments of the present disclosure will be described. The following embodiments of the present disclosure are each described as one example of the present disclosure. In addition, the present disclosure is not limited to the following embodiments and, in consideration of the claims and the entire specification, may be appropriately changed and/or modified within the scope of the present disclosure or within the range not against the concept thereof, and a treatment liquid composition, a set, an ink jet printing method, and a cloth, each of which is changed and/or modified as described above, are to be understood to be included in the technical scope of the present disclosure.

Treatment Liquid Composition

A treatment liquid composition (hereinafter, also simply referred to as “treatment liquid” in some cases) according to this embodiment is a treatment liquid composition which is used to be adhered to a cloth and which contains a cationic compound, a water-soluble resin, and water. In addition, the molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum peak in a molecular weight range of 28,000 to 2,800,000, and the content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to the total mass of the treatment liquid composition.
When a printed material is formed by adhering an ink composition to a cloth, the treatment liquid composition according to this embodiment is preferably adhered in advance to a cloth functioning as a substrate of the printed material. As the ink composition, an ink composition which will be described later may be used. In particular, as the ink composition, when a pigment-printing ink jet ink composition is used, by the treatment liquid composition according to this embodiment, a pigment is likely to be retained on a surface of the cloth. Because of the characteristics described above, the chromogenic property of the pigment of the printed material can be improved. Hence, the treatment liquid composition according to this embodiment is preferably a treatment liquid composition for pigment printing and is more preferably a treatment liquid composition for ink jet pigment printing.
Hereinafter, individual components contained in the treatment liquid composition according to this embodiment will be described. In addition, as an ink composition to be used for manufacturing a printed material, a pigment-printing ink jet ink composition (hereinafter, also simply referred to as “ink composition” in some cases) will be described by way of example.

Cationic Compound

The treatment liquid composition according to this embodiment contains a cationic compound. The cationic compound has a function to aggregate components in the ink composition. That is, in the case in which a printed material is manufactured, when the ink composition is adhered to a cloth to which the treatment liquid is adhered, the cationic compound contained in the treatment liquid works on particles of a pigment, resin particles (emulsion), and the like contained in the ink composition. As a result, the aggregation between the particles is promoted, and the particles are suppressed from being absorbed in spaces between fibers forming the cloth or in the fibers. Hence, color development of the pigment (colorant) of the printed material can be improved. Besides the effect described above, the cationic compound also has a function to increase the viscosity of the ink composition. Hence, excessive penetration of the ink composition in the cloth is suppressed, and in addition, the generation of blurring and bleeding can also be reduced.
The functions of the cationic compound described above are derived from an action which neutralizes a surface charge of the components contained in the ink composition or an action which changes the pH of the ink composition. By the action as described above, the aggregation or the precipitation of the pigment and the like in the ink composition and/or the increase in viscosity of the ink composition can be performed.
As the cationic compound, for example, a polyvalent metal salt or a cationic resin may be mentioned. Among those mentioned above, for example, since improving the chromogenic property of the pigment and being preferably used for a cotton cloth and a polyester cloth, a polyvalent metal salt is preferably used. Those cationic compounds may be used alone, or at least two types thereof may be used in combination.
The polyvalent metal salt is a water-soluble compound which contains a polyvalent metal cation having at least divalence and an anion forming a salt with the polyvalent metal cation. As the polyvalent metal cation having at least divalence, for example, there may be mentioned a divalent metal ion, such as Ca²⁺, Cu²⁺, Ni²⁺, Mg²⁺, Zn²⁺, or Ba²⁺, or a trivalent metal ion, such as Al³⁺, Fe³⁺, or Cr³⁺. In addition, as the anion, for example, there may be mentioned Cl⁻, I⁻, Br⁻, SO₄ ^2-, CO₃ ^2-, ClO₃ ⁻, NO₃ ⁻, HCOO⁻, or CH₃COO⁻. Among the polyvalent metal salts each formed from the polyvalent metal cation and the anion in combination as described above, in view of the improvement in storage stability of the treatment liquid and the improvement in chromogenic property by the function to aggregate the pigment and the resin particles (emulsion), a calcium salt or a magnesium salt is preferably used. As a preferable example of the calcium salt or the magnesium salt, there may be mentioned calcium nitrate, calcium chloride, or magnesium sulfate, and at least one of those mentioned above may be used. In particular, since the aggregation function is high, and the chromogenic property can be further improved, a calcium salt is more preferably used.
As the polyvalent metal salt, a hydrate thereof may also be used. As the hydrate of calcium chloride, for example, calcium chloride dihydrate may also be used, and as the hydrate of calcium nitrate, for example, calcium nitrate tetrahydrate may also be used. The polyvalent metal salts may be used alone, or at least two types thereof may be used in combination. When at least two types of polyvalent metal salts are used in combination, a calcium salt and a magnesium salt are preferably used in combination. In the case as described above, the aggregation function to aggregate the pigment and/or the resin particles (emulsion) is likely to be controlled. Since the aggregation function is prevented from being excessively enhanced, granularity of an image of the printed material can be suppressed from being likely to be generated, and as a result, irregularity of color development of the image can be reduced. As the magnesium salt, magnesium sulfate is preferably used.
As the cationic compound, besides the polyvalent metal salt, a metal salt other than the polyvalent metal salt may also be used. As the metal salt described above, sodium sulfate or potassium sulfate may be mentioned, each of which is formed using a monovalent metal cation, such as Na⁺ or K⁺, and the anion mentioned above in combination.
As the cationic resin, for example, an urethane resin, an olefin resin, or an allylamine resin, each of which has a cationic property, may be mentioned.
As the cationic urethane resin, for example, a known product or a commercially available product may be used. The cationic urethane resin may be used after being dissolved in a solvent, such as water or an organic solvent, or after being dispersed in the above solvent to form an emulsion. As the cationic urethane resin described above, for example, there may be mentioned Hydran (registered trademark) CP-7010, 7120, 7030, 7040, 7050, 7060, or 7610 (trade name, available from DIC Corporation); Superflex (registered trademark) 600, 610, 620, 630, 640, or 650 (trade name, available from DKS Co., Ltd.); or Urethane Emulsion WBR-2120C or 2122C (trade name, manufacture by Taisei Fine Chemical Co., Ltd.).
The cationic olefin resin is a high molecular weight compound which is derived form an olefin monomer and which has a structure, such as an ethylene chain or a propylene chain, as a primary skeleton. As the cationic olefin compound, a known product or a commercially available product may be used, and a cationic olefin resin dissolved in a solvent, such as water or an organic solvent, or dispersed in the solvent mentioned above to form an emulsion may also be used. As the cationic olefin resin described above, for example, there may be mentioned Arrow Base (registered trademark) CB-1200 or CD-1200 (trade name, available from Unitika Ltd.).
As the cationic allylamine resin, a known product may be used, and for example, there may be mentioned a polyallylamine hydrochloride, a polyallylamineamide sulfate, an allylamine hydrochloride-diallylamine hydrochloride copolymer, an allylamine acetate-diallylamine acetate copolymer, an allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, an allylamine-dimethylallylamine copolymer, a polydiallylamine hydrochloride, a polymethyldiallylamine hydrochloride, a polymethyldiallylamineamide sulfate, a polymethyldiallylamine acetate, a polydiallylmethylammonium chloride, a diallylamine acetate-sulfur dioxide copolymer, a diallylmethylethylammoniumethyl sulfate-sulfur dioxide copolymer, a methyldiallylamine hydrochloride-sulfur dioxide copolymer, a diallyldimethylammonium chloride-sulfur dioxide copolymer, or a diallydimethylammonium chloride-acrylamide copolymer.
As the cationic allylamine resin described above, a commercially available product may also be used, and for example, there may be mentioned PAA-HCl-01, 03, 05, 3L, 10L, PAA-H-HCL, PAA-SA, PAA-01, 03, 05, 08, 15, 15C, 25, PAA-H-10C, PAA-D11-HCl, PAA-D41-HCl, PAA-D19-HCl, PAS-21CL, 22SA, 92, 92A, PAS-M-1, 1L, LA, PAS-H-1L, 5L, 10L, PAS-J-81 or 81L (trade name, available from Nittobo Medical Co., Ltd.); Himoloc (registered trademark) NEO-600, Q-101, Q-311, Q-501, or Himax SC-505 (trade name, available from Hymo Corporation).
In addition, besides the cationic resin and the polyvalent metal salt described above, as other cationic compounds, for example, there may also be used a cationic surfactant, an inorganic acid, or an organic acid.
As the cationic surfactant, for example, there may be mentioned a primary, a secondary, or a tertiary amine chloride, an alkylamine salt, a dialkylamine salt, an aliphatic amine salt, a benzalkonium salt, a quaternary ammonium salt, a quaternary alkylammonium salt, an alkylpyridinium salt, a sulfonium salt, a phosphonium salt, an onium salt, or an imidazolinium salt. As a concrete example of the cationic surfactant as described above, for example, there may be mentioned a hydrochloride or an acetate of laurylamine, coconut amine, or rosin amine, dodecyltrimethylammonium chloride (lauryltrimethylammonium chloride), hexadecyltrimethylammonium chloride (cetyltrimethylammonium chloride), benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammonium ethyl sulfate, dimethylethyloctylammonium ethyl sulfate, trimethyllaurylammonium hydrochloride, cetylpyridinium chloride, cetylpyridinium bromide, dihydroxyethyllaurylamine, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylammonium chloride, hexadecyldimethylammonium chloride, or octadecyldimethylammonium chloride. As the cationic surfactants mentioned above, commercially available products may also be used.
As the inorganic acid or the organic acid, for example, there may be mentioned an inorganic acid, such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid; an organic acid, such as a 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, a sulfonic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, or nicotine acid; or a derivative or a salt of each of those mentioned above. Those acids may be used alone, or at least two types thereof may be used in combination.
As another cationic compound, for example, there may be used an inorganic pigment, such as choke, kaolin, calcined clay, talc, titanium oxide, zinc oxide, zinc sulfide, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, calcium montmorillonite, sodium montmorillonite, or bentonite; or an organic pigment, such as acrylic-based plastic pigment or an urea polymer compound.
The content of the cationic compound contained in the treatment liquid is not particularly limited and is, with respect to the total mass of the treatment liquid, preferably 0.1 to 40.0 percent by mass, more preferably 2.0 to 25.0 percent by mass, further preferably 3.0 to 15.0 percent by mass, and particularly preferably 5.0 to 10.0 percent by mass. Since the content of the cationic compound is set in the range described above, for example, the precipitation and/or the separation of the cationic compound in the treatment liquid is suppressed, and the aggregation of the pigment and/or the resin particles (emulsion) in the ink composition is promoted, so that the pigment and/or the resin particles (emulsion) are suppressed from being incorporated in the spaces between the fibers forming the cloth or in the fibers. As described above, by a sealing effect which enables the components of the ink composition and the like to stay in the vicinity of the surface of the cloth, a phenomenon (strike-through) in which the pigment (colorant) is allowed to pass in a rear surface direction of the printed material can be reduced, and the chromogenic property of the pigment in the printed material can be improved.

Water-Soluble Resin

The treatment liquid composition according to this embodiment contains a water-soluble resin. Since the water-soluble resin is contained, molecular chains of the water-soluble resin are likely to be entangled with the fibers of the cloth, and in addition, the viscosity of the treatment liquid composition tends to be relatively increased. Accordingly, when the treatment liquid composition is adhered to the cloth, the water-soluble resin has a function to enable the treatment liquid composition to be likely to be retained on the surface of the cloth. In particular, since fibers of a polyester cloth have a low hydrophilic property as compared to that of a cotton cloth, an aqueous treatment liquid composition or an aqueous ink composition is liable to be repelled by the fibers of the polyester cloth. Hence, the treatment liquid composition is not likely to be fixed to the polyester cloth as compared to that of the cotton cloth. However, since containing the water-soluble resin composition, the treatment liquid composition can be more preferably retained on the surface of the cloth.
In addition, in order to improve air permeability, in general, since the polyester cloth is formed with large (loose) stitches, the ink composition is more likely to penetrate in the cloth in some cases. However, since containing the water-soluble resin composition, the treatment liquid composition can be preferably retained on the surface of the cloth. Furthermore, when the ink composition is adhered to the cloth to which the treatment liquid composition is adhered, the water-soluble resin is dissolved in the ink composition, and the viscosity thereof is increased. By the increase in viscosity, the fluidity of the ink composition is degraded, and the ink composition is not likely to penetrate in the cloth and is likely to stay on the surface of the cloth. As a result, the ink composition stays on the surface of the cloth, so that a preferable color development can be obtained.
As the water-soluble resin, for example, there may be mentioned a nonionic resin, an anionic resin, or a cationic resin. In addition, in this specification, the cationic resin may correspond to both the above cationic compound and water-soluble resin.
In addition, in this specification, the “water-soluble” indicates a property in which an object material can be dissolved in ion-exchanged water at 20° C. at a concentration of 3 percent by mass or more, and in addition, the object material is dissolved preferably at a concentration of 5 percent by mass or more, more preferably at a concentration of 10 percent by mass or more, and further preferably at a concentration of 25 percent by mass or more.
As the water-soluble resin, at least one selected from a poly(ethylene oxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and a poly(vinyl pyrrolidone) is preferably contained. Among those resins mentioned above, a poly(ethylene oxide) and a poly(vinyl pyrrolidone), each of which is a nonionic resin, are preferable, and a poly(vinyl pyrrolidone) is more preferable. A poly(vinyl pyrrolidone) is more likely to be dissolved in the ink composition to increase the viscosity thereof and is likely to improve the color development. In addition, a poly(vinyl pyrrolidone) has a low spinnability, and hence, a coating property of the treatment liquid composition is likely to be improved.
As the poly(ethylene oxide) (hereinafter, also referred to as “polyethylene oxide” in some cases), a commercially available product may also be used, and for example, there may be mentioned PEO (registered trademark)-1, 2, 3, 4, 8, 15, 18, 27, or 29 (trade name, available from Sumitomo Seika Chemicals Company, Limited.); or 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, or R-1000 (trade name, available from Meisei Chemical Works, Ltd.).
In addition, the poly(ethylene oxide) is not limited to a homopolymer, and for example, a copolymer of ethylene oxide and another monomer, such as a copolymer of ethylene oxide and propylene oxide, may also be used.
Although the weight average molecular weight of the poly(ethylene oxide) is not particularly limited, a molecular weight of 1,000 to 6,000,000 is preferable, and a molecular weight of 10,000 to 5,500,000 is more preferable. Since the weight average molecular weight is set in the range described above, the viscosity of the treatment liquid is likely to be increased, and in addition, the molecular chains are likely to be entangled with the fibers of the cloth. In addition, the weight average molecular weight of the water-soluble resin, such as a poly(ethylene oxide), may be measured by a known method, such as gel filtration chromatography (GFC) or a gel permeation chromatography (GPC).
As the carboxymethyl cellulose, a commercially available product may also be used, and for example, there may be mentioned a sodium salt of the carboxymethyl cellulose, such as CMC Daicel (registered trademark) 1120, 1130, 1220, 1240, 1250, or 1330 (trade name, available from Daicel FineChem Ltd.); Cellogen (registered trademark) 5A, 6A, 7A, PL-15, F-5A, F-7A, F-907A, F-815A, or PR-S (trade name, available from DKS Co., Ltd.).
As the hydroxyethyl cellulose, a commercially available product may also be used, and for example, there may be mentioned HEC Daicel (registered trademark) SP200, SP400, SP500, SP600, SP850, SP900, SE400, SE550, SE600, SE850, SE900, or EE820 (trade name, available from Daicel FineChem 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, or CF-Y (trade name, available from Sumitomo Seika Chemicals Company, Limited.).
As the poly(vinyl pyrrolidone), a commercially available product may also be used, and for example, there may be mentioned a commercially available chemical reagent Polyvinylpyrrolidone K-30 or K-30W (trade name, available from Nippon Shokubai Co., Ltd.); PITZCOL (registered trademark) K-17L, K-30, K-30L, K-30AL, K-60L, K-50, or K-90, CREEJUS (registered trademark) K-30, or AIPHTACT (registered trademark) K-30PH (trade name, available from DKS Co., Ltd.); or PVP K-30, PVP K-25, or PVP K-17 (trade name, available from Ashland Inc.). In addition, the poly(vinyl pyrrolidone) is not limited to a homopolymer, and a copolymer of vinyl pyrrolidone and another monomer may also be used.
Although the glass transition temperature of the water-soluble resin described above is not particularly limited, the glass transition temperature is preferably −80° C. to 0° C. or more preferably −80° C. to −10° C. Since the glass transition temperature of the water-soluble resin is set in the range described above, in a printed material to which printing is performed, the texture of the substrate can be maintained, and in addition, for example, abrasion fastness can also be improved.
As another water-soluble resin, for example, there may also be used a hydroxypropyl methyl cellulose, a cellulose acetate, or a poly(vinyl alcohol).
The content of the water-soluble resin with respect to total mass of the treatment liquid composition is preferably 0.3 to 7.0 percent by mass, more preferably 0.5 to 6.0 percent by mass, and further preferably 0.6 to 5.0 percent by mass. Since the content is set in the range described above, the sealing effect of the treatment liquid composition on the cloth can be obtained, and in addition, the chromogenic property of the pigment can be further improved. This effect can be more preferably obtained when a polyester cloth having relatively large stitches is used. In addition, the cloth to which the treatment liquid composition is adhered is suppressed from being hardened, and the texture of the cloth can be maintained.
The treatment liquid composition according to this embodiment contains 0.6 to 5.0 percent by mass of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 with respect to the total mass of the treatment liquid composition. By the structure as described above, the water-soluble resin is likely to be dissolved in the ink composition on the cloth, and in addition, the viscosity of the ink composition is preferably increased. By the increase in viscosity thereof, the fluidity of the ink composition is degraded, and the ink composition is not likely to penetrate in the cloth and is likely to stay on the surface of the cloth. As a result, the color development of the ink composition can be improved.
The molecular weight of the water-soluble resin is preferably 30,000 to 2,700,000 and more preferably 32,000 to 2,600,000. Since the molecular weight range of the water-soluble resin is higher than the lower limit, an effect to preferably increase the viscosity of the ink composition adhered to the cloth can be obtained, and hence, an excellent chromogenic property can be preferably obtained. Since the molecular weight range of the water-soluble resin is lower than the upper limit, the treatment liquid composition has a preferable viscosity, and at a portion to which the treatment liquid composition is adhered, the treatment liquid composition is preferably not likely to generate a scar. In this case, the scar is generated as a coating scar which is observed after the coating due to the different in appearance, such as the change in hue, between the portion to which the treatment liquid composition is adhered and a portion to which no treatment liquid composition is adhered.
The treatment liquid composition according to this embodiment preferably contains a water-soluble resin having a molecular weight of 1,000 to 25,000. Since the water-soluble resin as described above is contained, the chromogenic property is further improved. Since the water-soluble resin as described above has a molecular weight smaller than the water-soluble resin having a molecular weight of 28,000 to 2,800,000, although the effect to increase the viscosity of the ink composition is low, this water-soluble resin is rapidly dissolved in the ink composition, and hence, an effect to rapidly increase the viscosity thereof is obtained immediately after the ink composition is adhered. Hence, when the water-soluble resin having a molecular weight of 1,000 to 25,000 and the water-soluble resin having a molecular weight of 28,000 to 2,800,000 are used in combination, the chromogenic property can be further improved. When the water-soluble resin having a molecular weight of 1,000 to 25,000 is contained, the content thereof with respect to the total mass of the treatment liquid composition is preferably 0.1 to 5.0 percent by mass, more preferably 0.2 to 4.0 percent by mass, and further preferably 0.5 to 2.0 percent by mass.
In this specification, the molecular weight of the water-soluble resin is a molecular weight measured by the GPC method described above and is a molecular weight with respect to that of a standard product. The measurement of the molecular weight may be performed either on the water-soluble resin itself or on the treatment liquid composition. In this case, the components contained in the treatment liquid composition are preferably identified in advance.
In addition, in this specification, the “water-soluble” indicates the property described above, and the “water-soluble component” indicates a component having a water solubility among the components contained in the treatment liquid composition. In more particular, although the water-soluble component is represented by the water-soluble resin described above, the water-soluble component is not limited thereto, and among the cationic compounds, a compound having a water solubility may also be included.

Water

The treatment liquid composition according to this embodiment contains water as a primary solvent. This water is a component which is evaporated and removed by drying performed after the treatment liquid is adhered to the substrate, such as the cloth. As the water, for example, there may be used purified water, such as ion-exchanged water, ultrafiltration water, reverse osmosis water, or distilled water, or water, such as ultrapure water, in which ionic impurities are removed as much as possible. In addition, when water which is sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, in the case in which the treatment liquid is stored for a long time, the generation of fungi and bacteria can be suppressed. In addition, the primary solvent of the treatment liquid composition is not limited to water, and for example, a water-soluble organic solvent may also be used as the primary solvent.
The content of the water contained in the treatment liquid composition with respect to the total mass (100 percent by mass) of the treatment liquid composition may be set, for example, to 50 percent by mass or more, and is preferably 60 to 99 percent by mass, more preferably 70 to 98 percent by mass, and further preferably 80 to 95 percent by mass. Since the content of the water is set in the range described above, the increase in viscosity of the treatment liquid composition is suppressed, and in addition, the workability obtained when the treatment liquid composition is adhered to the cloth and the drying property obtained after the treatment liquid composition is adhered thereto can be improved. In addition, the water of the treatment liquid includes water which is used as a raw material of the treatment liquid, such as water blended in a resin emulsion which will be described later.

Water Repellant

The treatment liquid composition according to this embodiment preferably contains a water repellant. In this specification, the water repellant indicates an additive which is used to impart a repellent property to a cloth surface to which the treatment liquid composition is adhered. When the treatment liquid composition contains a water repellant, since the repellent property can be imparted to the cloth surface to which the treatment liquid composition is adhered, an ink composition containing water as a primary solvent is likely to stay on the surface of the cloth, and hence, the chromogenic property can be improved. In particular, when the water repellant is used together with the water-soluble resin described above, during a period immediately after the ink composition is adhered to the generation of the sealing effect by the increase in viscosity of the water-soluble resin, the ink composition can be allowed to stay on the cloth surface, and hence, the chromogenic property can be further improved.
The water repellant is a compound having a hydrophilic portion and a hydrophobic portion and may be in the form of particles, and by the use of the water repellant as described above, the water repellant is selectively oriented on the surface of a coating film, so that various functions, such as a water repellent property and a slip property, can be obtained. The water repellant as described above is not particularly limited, and for example, there may be mentioned calcium stearate, ammonium stearate, a silicone-based water repellant, a fluorine-based water repellant, a polyethylene wax, a paraffin wax, a carnauba wax, or a polyethylene-paraffin wax. Those water repellants mentioned above may be used alone, or at least two types thereof may be used in combination.
Among the water repellants mentioned above, in order to more effectively and reliably obtain the effect of the present disclosure, the water repellant is preferably at least one selected from a fluorine-based water repellant, a silicone-based water repellant, and a paraffin wax resin. The water repellant may be in the form of an oxide or in the form of a derivative incorporating a functional group, such as a carboxyl group. In addition, since the viscosity can be further decreased, the water repellant is preferably in the form of resin particles (emulsion). As the type of emulsion, for example, an emulsion polymerization type, a forced emulsion type, and a self emulsion type may be mentioned. When the water repellant is in the form of resin particles, for example, since the viscosity is decreased, a film forming property is improved, and even when the water repellant is added to the treatment liquid composition at a low concentration, the uniformity in an adhesion surface is improved. In addition, the water repellant is not likely to be dissolved in the ink composition, and hence, a preferable repellent property is likely to be obtained.
In this embodiment, the water repellant is preferably a resin having a melting point of 150° C. or less, more preferably a resin having melting point 100° C. or less, and further preferably a resin having a melting point of 70° C. to 100° C. Since the melting point of the water repellant is 150° C. or less, the film forming property obtained when the treatment liquid composition is adhered to the cloth is preferable, and even when the water repellant is added to the treatment liquid composition at a low concentration, the uniformity in the adhesion surface is improved. In addition, since the melting point of the water repellant is 70° C. or more, the water repellant is not likely to be dissolved in the ink composition, and hence, a preferable repellent property is likely to be obtained.
As the water repellant described above, a commercially available product may also be used, and for example, there may be mentioned AQUACER (registered trademark) 497, 537, or 539 (trade name, manufactured by BYK Japan KK, paraffin wax); SFCOAT (registered trademark) SWK-601 (trade name, manufactured by AGC SEIMI CHEMICAL CO., LTD., fluorine-based water repellant).
In this embodiment, the content of the water repellant with respect to the total mass of the treatment liquid composition is preferably 0.01 to 5.0 percent by mass, more preferably 0.01 to 0.30 percent by mass, and further preferably 0.05 to 0.10 percent by mass. Since the content of the water repellant is 0.01 percent by mass or more, the chromogenic property of the ink composition can be further improved, and since the content of the water repellant is 5 percent by mass or less, the granularity of the image can be reduced, and the irregularity of color development of the image can be reduced.

Resin Particles

The treatment liquid composition according to this embodiment preferably contains resin particles. In this specification, the resin particles are preferably resin particles different from those of the water repellant, and as a material forming the resin particles, an urethane-based resin, a vinyl acetate-based resin, an acrylic-based resin, a styrene-acrylic-based resin, or a polyester-based resin is preferable, and at least one of those mentioned above is preferably used. By the use of the resin particles, fixability of the colorant (pigment) contained in the ink composition to the cloth can be further improved. In addition, as a sealing agent which suppresses the treatment liquid composition and/or the ink composition from excessively penetrating (infiltrating) in the cloth, the resin particles may also be used.
When the treatment liquid composition uses water as a primary solvent as is the case of this embodiment, the resin particles may be used as a resin emulsion in which the resin particles are dispersed in an aqueous solvent. As a method for dispersing the resin particles, a forced emulsion type using an emulsifier (surfactant) or a self emulsion type incorporating a hydrophilic portion (hydrophilic group) in a molecular structure of the resin particles may be used. In addition, the resin particles may have a reactivity (cross-linking reactivity), and for example, resin particles having an isocyanate group masked by a blocking agent in the molecular structure may also be used.
The average particle diameter of the resin particles is preferably 30 to 300 nm and more preferably 40 to 100 nm. When the average particle diameter is set in the range described above, the dispersibility of the resin emulsion in the treatment liquid composition and the fixability thereof to the cloth can be improved. In addition, in this specification, the “average particle diameter” indicates a volume-basis particle size distribution (50%) unless otherwise particularly noted. The average particle diameter is measured by a dynamic light scattering method or a laser diffraction method described in JIS 28825. In particular, a particle size distribution meter (such as “Microtrac UPA” available from Nikkiso Co., Ltd.) using a dynamic light scattering method as a measurement principle may be used.
As the resin emulsion described above, a commercially available product may also be used. For example, as the urethane-based resin emulsion, for example, there may be mentioned Superflex (registered trademark) 150, 420, 460, 470, 500, 610, 700, 800, 870, 6E-2000, E-2500, E-4000, or R-5000 (trade name, available from DKS Co., Ltd.); Adeka Bontaita (registered trademark) HUX-290K, 380, 822, or 830 (trade name, available from ADEKA Corporation); Takelac (registered trademark) W-6020, 6021, 6061, 605, 635, or WS-6021 (trade name, available from Mitsui Chemicals Polyurethanes, Inc.); Permarin (registered trademark) UA-150 (trade name, available from Sanyo Chemical Industries, Ltd.); Suncure (registered trademark) 2710 (trade name, available from Nippon Lubrizol); or NeoRez (registered trademark) R-940, 9637, or 9660 (trade name, available from Kusumoto Chemicals, Ltd.).
As the vinyl acetate-based resin emulsion, for example, there may be mentioned Vinyblan (registered trademark) 1245L (trade name, available from Nisshin Chemical Industry Co., Ltd.); Polysol (registered trademark) SH-502, AD-2, 10, 13, 17, 70, or 96 (trade name, available from Showa Denko K.K.); or Seikadyne (registered trademark) 1900W (trade name, available from Dainichiseika Color & Chemicals Mfg. Co., Ltd.).
As the acrylic-based resin emulsion, for example, there may be mentioned Voncoat (registered trademark) AN-402, R-3310, R-3360, or 4001 (trade name, available from DIC Corporation); Polysol (registered trademark) AM-710, 920, 2300, AP-4735, AT-860, or PSASE-4210E (trade name, Showa Denko K.K.); Saivinol (registered trademark) SK-200 (trade name, available from Saiden Chemical Industry Co., Ltd.); AE-120A (trade name, available from JSR Corporation); Vinyblan (registered trademark) 2650, 2680, 2682, 2684, 2886, or 5202 (trade name, available from Nisshin Chemical Industry Co., Ltd.); or NK-Binder R-5HN (trade name, available from Shin Nakamura Chemical Co., Ltd.).
As the styrene-acrylic-based resin emulsion, for example, there may be mentioned Microgel (registered trademark) E-1002 or 5002 (trade name, available from Nippon Paint Co., Ltd.); Voncoat (registered trademark) 5454 (trade name, available from DIC Corporation); Polysol (registered trademark) AP-7020 (trade name, available from Showa Denko K.K.); SAE1014 (trade name, available from Zeon Corporation); AE373D (trade name, available from Emulsion Technology Co., Ltd.); 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, or 7630A (trade name, available from BASF); Movinyl (registered trademark) 966A or 7320 (trade name, available from Nippon Synthetic Chemical Industry Co., Ltd.).
As the polyester-based resin emulsion, for example, there may be mentioned Elytel (registered trademark) KA-50715, KT-8701, 8803, 8904, 9204, or 0507 (trade name, available from Unitika Ltd.); or Hytec SN-2002 (trade name, available from Toho Chemical Industry Co., Ltd.).
Among the resin emulsions described above, in order to suppress a reaction with a cationic polymer, a nonionic or a cationic resin emulsion is more preferably used.
When the resin particles are used for the treatment liquid composition, the content (content of the resin emulsion based on a solid component) with respect to the total mass of the treatment liquid composition is preferably 0.1 to 20.0 percent by mass, more preferably 0.1 to 7.0 percent by mass, and further preferably 0.5 to 1.0 percent by mass. Since the content of the resin particles based on the solid component is set in the range described above, while the degradation in storage stability and the increase in viscosity of the treatment liquid composition are suppressed, washing fastness, abrasion fastness, and the like of the printed material can be improved.

Surfactant

To the treatment liquid composition, a surfactant may be further added. The surfactant has a function to decrease the surface tension of the treatment liquid composition and to increase a penetration property in the cloth. As the surfactant, for example, there may be mentioned a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an ampholytic surfactant, and at least one of those surfactants may be used. In particular, since the function of the above cationic compound is not likely to be disturbed, a nonionic surfactant is preferably used.
When the surfactant is added to the treatment liquid composition, the content of the surfactant with respect to the total mass of the treatment liquid composition is preferably 2.0 percent by mass or less, more preferably 1.5 percent by mass or less, and further preferably 1.1 percent by mass or less. Since the content of the surfactant is set in the range described above, the surface tension of the treatment liquid composition is suppressed from being excessively decreased, and when the treatment liquid composition is adhered to the cloth, the treatment liquid composition is likely to be retained on the surface of the cloth. Accordingly, the function of the treatment liquid composition can be easily obtained. In addition, when the surfactant is added, the lower limit of the content of the surfactant with respect to the total mass of the treatment liquid composition is preferably 0.01 percent by mass or more, more preferably 0.05 percent by mass or more, and further preferably 0.07 percent by mass or more. Since the content of the surfactant is set in the range described above, when the treatment liquid composition is adhered to the cloth, the wettability to the cloth can be improved.
As the fluorine-based surfactant, a commercially available product may be used, and for example, there may be mentioned Megafac (registered trademark) F-479 (trade name, available from DIC Corporation) or BYK-340 (trade name, available from BYK Japan KK).
Although the silicone-based surfactant is not particularly limited, a polysiloxane-based compound may be used. The polysiloxane-based compound is not particularly limited, and for example, a polyether modified organosiloxane may be mentioned. As a commercially available product of the polyether modified organosiloxane, for example, there may be mentioned BYK-302, 306, 307, 333, 341, 345, 346, 347, or 348 (trade name, available from BYK Japan KK); or KF-351A, 352A, 353, 354L, 355A, 615A, 945, 640, 642, 643, 6020, 6011, 6012, 6015, 6017, or X-22-4515 (trade name, available from Shin-Etsu Chemical Co., Ltd.).
As the anionic surfactant, for example, there may be mentioned a higher fatty acid salt, a soap, an α-sulfo fatty acid methyl ester salt, an alkylbenzene sulfonate, an alkyl sulfate ester salt, an alkyl ether sulfate ester salt, a monoalkyl phosphate ester salt, an α-olefin sulfonate, an alkylene naphthalene sulfonate, a naphthalene sulfonate, an alkane sulfonate, a polyoxyethylene alkyl ether sulfate, a sulfosuccinate, a polyoxyalkylene glycol alkyl ether phosphate ester salt.
As the cationic surfactant, for example, there may be mentioned a quaternary ammonium salt, such as an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, or an alkyldimethylbenzylammonium salt, or an amine salt compound, such as a N-methylbishydroxyethylamine fatty acid ester hydrochloride. In addition, as the cationic surfactant, the cationic compound described above may also be used.
The ampholytic surfactant is not particularly limited, and for example, an amino acid compound, such as an alkylamino fatty acid salt, may be mentioned.
As the nonionic surfactant, a polyoxyalkylene-based compound having the structure represented by the following formula (1) is preferably contained.
R⁴—O—X—H (1)
In the formula (1), R⁴represents a substituted or an unsubstituted hydrocarbon group having 16 carbon atoms or more, and X represents a polyoxyethylene skeleton or a polyoxypropylene skeleton.
In addition, among the compounds each having the structure represented by the above formula (1), a compound having the structure represented by the following formula (1-1) is also preferable.
R⁴—O—(CHR⁵—CHR⁶—O)_m—H (1-1)
In the formula (1-1), R⁴represents a substituted or an unsubstituted hydrocarbon group having 16 carbon atoms or more, R⁵and R⁶each independently represents hydrogen or a methyl group, one of R⁵and R⁶represents hydrogen, and m represents an integer of 2 to 20.
In the nonionic compound represented by the formula (1-1), one end terminal of a condensed chain of ethylene oxides or propylene oxides is a monoalkyl ether, and the other end terminal thereof is a hydroxide group. In the nonionic compound as described above, the condensed chain portion primarily has a hydrophilic property, and the alkyl group (R⁴) of the alkyl ether portion primarily has a hydrophobic property. Accordingly, this compound is able to have an activity as an emulsifier. In the compound represented by the formula (1-1), since R⁴has 16 carbon atoms or more, a sufficient hydrophobic property is obtained, and hence, it is believed that this compound is able to function as an emulsifier. In addition, R⁴more preferably has 18 carbon atoms or more. The upper limit of the number of carbon atoms is preferably 20 or less.
Since the compound as described above is used, the problems of the image quality, such as the granularity of the image and the generation of wind ripples, can be preferably suppressed. The reason for this is believed that the compound represented by the formula (1) stabilizes the dispersion system in the ink and preferably suppresses the reactivity with the cationic compound. For example, in a pigment printing ink, since a resin or the like which is the dispersion system in the ink reacts with the cationic compound, aggregation occurs, and hence, preferable chromogenic property and abrasion fastness are obtained; however, when this reaction is excessively fast, the aggregation occurs before dots wet spread, and a granular touch may be imparted to the image, or wind ripples may be generated in some case. In addition, when the ink is adhered at a low duty, the tendency described above may be more apparently recognized. In addition, when the viscosity of the treatment liquid composition is high, and/or when the hydrophobic property of the treatment liquid composition is excessively high, the wet spreadability is degraded, and the granular touch of the image is more liable to be generated. However, it is believed that since the compound represented by the formula (1) is contained, the reaction between the dispersion system in the ink and the cationic compound is appropriately suppressed, and the ink sufficiently wet spreads, so that the granularity of the image and the generation of wind ripples are appropriately suppressed.
As an example of the compound represented by the formula (1), for example, there may be mentioned a polyoxyethylene stearyl ether, a polyoxyethylene oleyl ether, or a polyoxyethylene lauryl ether. As a commercially available product corresponding to the compound described above, Emulgen 350 or Emulgen 420 (manufactured by Kao Corporation); or Newcol 1860, Newcol 1210, or Newcol 1204 (manufactured by Nippon Nyukazai Co., Ltd.). Among those compounds mentioned above, as the nonionic surfactant, a polyoxyethylene oleyl ether is preferably used.
In addition, as for the nonionic compound represented by the formula (1), an HLB (Hydrophilic-Lipophilic Balance) value can be defined, and when the nonionic compound represented by the formula (1) is used, the HLB value thereof is preferably 12 or more, more preferably 13 or more, and further preferably 15 or more. In this case, the HLB value is an HLB value defined by Griffin's method. As the compound described above, for example, there may be mentioned Emulgen 350 (polyoxyethylene stearyl ether, the carbon number of R⁴of the formula (1) is 18, the HLB value is 17.8), Emulgen 420 (polyoxyethylene oleyl ether, the carbon number of R⁴of the formula (1) is 18, the HLB value is 13.6), Newcol 1860 (polyoxyethylene stearyl ether, the carbon number of R⁴of the formula (1) is 18, the HLB value is 18.1), Newcol 1210 (polyoxyethylene oleyl ether, the carbon number of R⁴of the formula (1) is 18, the HLB value is 12.4), or Newcol 1204 (polyoxyethylene oleyl ether, the carbon number of R⁴of the formula (1) is 18, the HLB value is 7.9).
As another nonionic surfactant, for example, an acetylene glycol-based surfactant, a fluorine-based surfactant, or a silicone-based surfactant may also be used.
The acetylene glycol-based surfactant is not particularly limited, and for example, there may be mentioned 2,4,7,9-tetramethyl-5-decyne-4,7-diol, an alkylene oxide adduct of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,4-dimethyl-5-decyne-4-ol, an alkylene oxide adduct of 2,4-dimethyl-5-decyne-4-ol, or an alkylene oxide adduct of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3-ol, or 2,4-dimethyl-5-hexyne-3-ol.
As the acetylene glycol-based surfactant described above, a commercially available product may also be used. For example, there may be mentioned Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, or DF110D (trade name, available from 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, or AE-3 (trade name, available from Nisshin Chemical Industry Co., Ltd.); or Acetynol (registered trademark) E00, E00P, E40, or E100 (trade name, available from Kawaken Fine Chemicals Co., Ltd.).
The surfactants mentioned above may be used alone, or at least two types thereof may be used in combination. In addition, among those surfactants, a surfactant having an HLB (Hydrophilic-Lipophilic Balance) of 13 or more is preferably used. Accordingly, when the treatment liquid composition is adhered, the penetration and the wet spreading thereof with respect to the cloth can be adjusted.
As the surfactant, the nonionic surfactant is preferably used. Since having a nonionic property, the function of the cationic compound described above is not disturbed.

Other Components

To the treatment liquid composition, various additives, such as a pH adjuster, an antiseptic agent, a fungicide, an antioxidant, and a chelating agent, and various organic solvents may be added.
The pH adjuster is not particularly limited, and for example, there may be mentioned an organic base or an inorganic base. As the organic base, for example, an alkanolamine, such as triethanolamine, diethanolamine, monoethanolamine, or tri-iso-propanolamine, may be mentioned. As the inorganic base, for example, a strong base, which is a hydroxide of an alkali metal or an alkaline earth metal, such as lithium hydroxide, potassium hydroxide, or calcium hydroxide, may be mentioned.
As the antiseptic agent and the fungicide, for example, there may be mentioned sodium benzoate, sodium pentachlorophenate, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, or 1,2-dibenzisothiazoline-3-one (PROXEL CRL, PROXEL BDN, PROXEL GXL, PROXEL XL-2, or PROXEL TN, trade name of Lonza). Since the antiseptic agent and/or the fungicide is added to the treatment liquid composition, bacteria and/or fungi can be suppressed from being bred in the treatment liquid composition.
The organic solvent may be added to adjust the physical properties, such as the viscosity and the surface tension, of the treatment liquid and the drying property of the treatment liquid composition. When the organic solvent is added, an organic solvent to be used for the ink composition described below may be used.

Method for Preparing Treatment Liquid Composition

The treatment liquid composition may be prepared in such a way that after the individual components described above are mixed together in an arbitrary order, if needed, the mixture thus obtained is filtrated to remove impurities and foreign materials. As a method for mixing the individual components, there may be used a method in which the materials (components) are sequentially charged in a container equipped with a stirring device, such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. As a filtration method, for example, centrifugal filtration or filter filtration may be used.

Physical Properties of Treatment Liquid Composition

The physical properties of the treatment liquid composition are arbitrarily adjusted in accordance with the type of cloth, the method (coating method) to adhere the treatment liquid composition to the cloth, and the like. The method for coating the treatment liquid composition will be described below.
The viscosity of the treatment liquid at 20° C. is not particularly limited, and for example, the viscosity thereof is set to preferably 0.5 to 100 mPa·s (millipascal·second), more preferably 1 to 50 mPa·s, and further preferably 1.5 to mPa·s. Since the viscosity of the treatment liquid composition is set in the range described above, when the treatment liquid composition is adhered to the cloth, the coating property, such as the spreadability, of the treatment liquid can be improved.
In addition, when an ink jet method is used as the coating method, the viscosity of the treatment liquid at 20° C. is set to preferably 0.5 to 15 mPa·s, more preferably 1 to 5 mPa·s, and further preferably 1.5 to 3.6 mPa·s. Since the viscosity of the treatment liquid composition for the ink jet method is set in the range described above, an ejection stability of the treatment liquid ejected from an ink jet head is improved, and in addition, the time of a step of adhering the treatment liquid can be decreased.
The viscosity of the treatment liquid composition is measured, for example, using a viscoelastic tester MCR-301 (manufactured by Anton Paar). In particular, the measurement may be performed in such a way that the temperature of the treatment liquid is controlled at 20° C., the shear rate is increased from 0.01 s⁻¹to 1.00 s⁻¹, and the viscosity at a shear rate of 0.10 s⁻¹is read.
The surface tension of the treatment liquid composition at 25° C. is, for example, set to preferably 30 to 60 mN/m and more preferably 35 to 50 mN/m. Since the surface tension of the treatment liquid composition at 25° C. is set in the range described above, when the treatment liquid composition is adhered to the cloth, the wettability to the cloth is improved, and in addition, the treatment liquid composition can be likely to be retained on the surface of the cloth.
The surface tension of the treatment liquid may be measured, for example, using an automatic surface tension meter CBVP-Z (available from Kyowa Interface Science Co., Ltd.). In particular, the measurement may be performed in such a way that in an environment at 25° C., the surface tension is read when a platinum plate is wetted with the treatment liquid.

Molecular Weight Distribution of Water-Soluble Component

The molecular weight distribution of the water-soluble component contained in the treatment liquid composition according to this embodiment has a maximum peak in a molecular weight range of 28,000 to 2,800,000. Accordingly, the water-soluble component is likely to be dissolved in the ink composition on the cloth, and in addition, the viscosity of the ink composition is preferably increased. By the increase in viscosity, since the fluidity of the ink composition is degraded, the ink composition is not likely to penetrate in the cloth and is likely to stay on the surface thereof. As a result, a preferable color development can be obtained by the ink composition.
The molecular weight distribution of the water-soluble component preferably has a maximum peak in a molecular weight range of 30,000 to 2,700,000 and more preferably has a maximum peak in a molecular weight range of 32,000 to 2,600,000. Since the molecular weight of the water-soluble component is higher than the lower limit, an effect to preferably increase the viscosity of the ink composition is obtained, and an excellent chromogenic property can be preferably obtained. Since the molecular weight of the water-soluble component is lower than the upper limit, the viscosity of the treatment liquid composition is preferable, and a coating scar of the treatment liquid composition is preferably not likely to be generated at a portion to which the treatment liquid composition is adhered.
Furthermore, the molecular weight distribution of the water-soluble component contained in the treatment liquid composition according to this embodiment also preferably has a maximum peak in a molecular weight range of 1,000 to 25,000, and the ratio of a peak area of a molecular weight of 28,000 to 2,800,000 to a peak area of a molecular weight of 1,000 to 25,000 is preferably 1:5 to 5:1. Accordingly, the chromogenic property is further improved. Since there is the peak in the range having a molecular weight smaller than that of the above molecular weight distribution (28,000 to 2,800,000), although the effect to increase the viscosity of the ink composition is low, the water-soluble component is more rapidly dissolved in the ink composition, and hence, an effect to increase the viscosity of the ink composition can be obtained immediately after ink composition is adhered. Hence, a preferable chromogenic property can be obtained.
In addition, since the ratio of the peak area having a molecular weight of 28,000 to U.S. Pat. No. 2,800,000 to the peak area having a molecular weight of 1,000 to 25,000 is 1:5 to 5:1, the viscosity of the treatment liquid composition is preferable. In addition, the rate of dissolution of the treatment liquid composition in the ink composition and the viscosity thereof after the dissolution are preferable, and hence, a preferable chromogenic property can be obtained. The molecular weight distribution preferably has a maximum peak in a molecular weight range of 1,200 to 22,000 and more preferably has a maximum peak in a molecular weight range of 1,500 to 21,000. In addition, the ratio of the peak area having a molecular weight of 28,000 to U.S. Pat. No. 2,800,000 to the peak area having a molecular weight of 1,000 to 25,000 is more preferably 1:4 to 4:1 and further preferably 1:3 to 3:1.
In addition, in the molecular weight distribution described above, the presence or absence of the maximum peak and the peak area may be obtained by the GPC method described above (also called a size-exclusion chromatography (SEC) method).

Ink Composition

Next, an ink composition will be described which is used to manufacture a printed material and which is to be printed on a cloth to which the treatment liquid composition according to this embodiment is adhered. The ink composition according to this embodiment is preferably an aqueous pigment ink for ink jet printing. Since the number of types of cloths to which the pigment ink can be applied is large, the pigment ink is more preferable than a dye ink. On the other hand, since penetrating in the cloth, the pigment ink is not likely to obtain the chromogenic property in some cases; however, when the treatment liquid composition of the present disclosure is used, the chromogenic property can be improved. In addition, as a printing method, since ink jet printing by an ink jet method is used, compared to related analog printing, for example, a highly fine image can be manufactured while the manufacturing cost thereof is reduced.
The ink composition to be used in this embodiment is a pigment-printing ink jet ink composition (hereinafter, simply referred to as “ink composition” in some cases) which contains a pigment, resin particles, and water. The ink composition used in this embodiment may form a set together with the treatment liquid composition according to this embodiment described above.
In addition, in the set, a white ink (white pigment-printing ink jet ink composition) containing a white pigment as the pigment is preferably included. In addition, in the set described above, besides the white ink, a color ink (color pigment-printing ink jet ink composition) containing a color pigment is preferably contained. In the case described above, in the ink jet pigment printing method which will be described later, dual-layer printing in which color printing is performed on a white underlayer can be performed. Hereinafter, first, components contained in the ink composition according to this embodiment will be described.

Colorant

The ink composition according to this embodiment uses a pigment as a colorant. Since the pigment is used as the colorant, compared to the case in which a dye is used, steps, such as a dyeing step and a washing step, can be simplified.
As the pigment, known organic pigments and inorganic pigments may be used. As the organic pigment, for example, there may be mentioned an azo pigment, such as an azo lake pigment, an insoluble azo pigment, a condensed azo pigment, or a chelate azo pigment; a polycyclic pigment, such as a phthalocyanine pigment, a perylene pigment, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, a thioindigo pigment, an isoindolinone pigment, an isoindoline pigment, a quinophthalone pigment, or diketopyrrolopyrrole pigment; a dye chelate pigment, such as a basic dye lake or an acidic dye lake; a nitro pigment, a nitroso pigment, an aniline black, or a daylight fluorescent pigment. As the inorganic pigment, for example, there may be mentioned a metal oxide pigment, such as titanium dioxide, zinc oxide, or chromium oxide, or a carbon black. In addition, a glitter pigment, such as a pearl pigment or a metallic pigment, may also be used.
As the pigments mentioned above, for example, as a pigment for black pigment ink, C.I. (Colour Index Generic Name) Pigment Black 1, 7, or 11 may be mentioned. Among those mentioned above, for the ink jet printing, a carbon black base (C.I. Pigment Black 7) which has a relatively low specific gravity and which is not likely to precipitate in an aqueous medium is preferable.
For the color pigment ink (color ink), for example, there may be mentioned 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, or 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, 63:1, 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, or 219; C.I. Pigment Violet 19 or 23; C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60, or 63; C.I. Pigment Green 1, 4, 7, 8, 10, 17, 18, or 36. The average particle diameter of the pigment mentioned above is preferably 5 μm or less, more preferably 0.3 μm or less, and further preferably in a range of 0.01 to 0.15 μm. Since the average particle diameter of the pigment is set in the range described above, the ejection stability of the ink composition ejected from the ink jet head can be secured, and in addition, the chromogenic property of the pigment in the printed material can be improved.
Since the chromogenic property of the pigment is improved, the treatment liquid composition according to this embodiment is more preferably used to print a white ink containing a white pigment. In particular, for example, when a color image is printed on a color cloth colored in advance, a method in which a white ink is first printed to form an underlayer may be mentioned. This method is performed in order to suppress the influence of the color (color of the substrate) of the cloth on a color image to be printed and to improve the color development thereof. That is, when the treatment liquid composition according to this embodiment and the white ink are used together, an underlayer having a shielding property which is improved by the chromogenic property of the white pigment is formed, and regardless of the color of the substrate, for example, an image having a desired color tone may be printed.
As the white pigment for white ink, for example, there may be mentioned C.I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium dioxide), 6:1 (titanium dioxide containing another metal oxide), 7 (zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (mica titanium), 21 (barium sulfate), (plaster), 26 (magnesium oxide.silicon dioxide), 27 (silicon dioxide), or 28 (anhydrous calcium silicate). Among those mentioned above, C.I. Pigment White 6 having excellent chromogenic property, shielding property, and the like is preferably used.
The average particle diameter of the white pigment is preferably 100 to 450 more preferably 200 to 400 and further preferably 250 to 380 μm. Since the average particle diameter of the white pigment is set in the range described above, the ejection stability of the white ink ejected from the ink jet head can be secured, and in addition, the shielding property for the color of the cloth substrate can be improved.
For the measurement of the average particle diameter of the pigment, a method similar to that of the average particle diameter of the resin particles described above may also be used.
When the pigment is used, the content thereof is not particularly limited, and for example, the content with respect to the total mass of the pigment ink is preferably set to 0.1 to 50.0 percent by mass, more preferably set to 1.0 to 20.0 percent by mass, and further preferably set to 1.0 to 15.0 percent by mass. Since the content of the pigment is set in the range described above, in the printed material in which printing is performed, the chromogenic property of the pigment can be secured, and in addition, the increase in viscosity of the ink composition and the generation of clogging in the ink jet head can be suppressed.
The pigments mentioned above may be used alone, or at least two types thereof may be used in combination. In order to improve the dispersibility of the pigment in the ink composition, a surface treatment is preferably performed on the pigment, or a dispersant is preferably blended in the ink composition. The surface treatment of the pigment is a method in which by a physical treatment or a chemical treatment, a hydrophilic group, such as a carboxyl group or a sulfo group, is incorporated on the particle surface of the pigment. By the surface treatment of the pigment, the pigment can be dispersed in an aqueous medium, such as water.
The dispersant used for the aqueous medium has a function in which a hydrophobic portion (hydrophobic group) in the molecular structure is adsorbed on the particle surface of the pigment and a hydrophilic portion (hydrophilic group) is oriented at a medium side. By the function described above, the pigment can be dispersed in the aqueous medium. As the dispersant, known surfactants and high molecular weight materials may be used. In addition, a method in which the dispersibility is imparted by covering the pigment particles with a high molecular weight compound may also be used. As a method for covering the pigment particles, for example, an acid deposition method, a phase transfer emulsification method, or a mini-emulsion polymerization method may be used.

Water

The ink composition used in this embodiment is preferably an aqueous ink. When an aqueous ink composition is used, water is a primary solvent of the ink composition according to this embodiment. When the ink composition is adhered, water is evaporated and removed from the cloth by drying. As the water, water similar to that used for the treatment liquid composition described above may also be used. The content of the water contained in the ink composition with respect to the total mass of the ink composition is, for example, 30 to 90 percent by mass, preferably 40 to 85 percent by mass, and more preferably 50 to 80 percent by mass. Since the content of the water is set in the range described above, the increase in viscosity of the ink composition can be suppressed. In addition, in this specification, the “aqueous ink” indicates an ink composition, the water content of which is 30 percent by mass or more with respect to the total mass of the ink composition.

Organic Solvent

To the ink composition, an organic solvent may be added. By the addition of the organic solvent, the physical properties, such as the viscosity and the surface tension, and the behaviors, such as drying and penetration, observed when the ink composition is adhered to the cloth can be adjusted. As the organic solvent, for example, there may be mentioned a 2-pyrrolidone, a 1,2-alkanediol, a polyvalent alcohol, or a glycol ether. Those organic solvents may be used alone, or at least two types thereof may be used in combination.
The 2-pyrrolidone indicates a compound having a 2-pyrrolidone skeleton. As the 2-pyrrolidone, for example, besides a 2-pyrrolidone having no substituent, a compound having a substituent, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or N-vinyl-2-pyrrolidone, may be mentioned. As the substituent in the 2-pyrrolidoen skeleton, an organic group, such as a saturated or an unsaturated hydrocarbon group, having 1 to 5 carbon atoms is preferable. Among those compounds mentioned above, 2-pyrrolidone, which has an excellent storage stability of the ink composition and an excellent effect to suppress the generation of aggregates, is more preferably used.
As the 1,2-alkanediol, for example, there may be mentioned 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, or 1,2-octanediol. The 1,2-alkanediol improves the wettability of the ink composition to the cloth and has an excellent function to uniformly wet the cloth. Hence, an image suppressing the generation of blurring can be formed. The content of the 1,2-alkanediol to be added is preferably 1 to 20 percent by mass with respect to the total mass of the ink composition.
As the polyvalent alcohol, for example, there may be mentioned 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-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, or glycerin. By the addition of the polyvalent alcohol to the ink composition, drying and solidification of the ink composition in an ejection nozzle of the ink jet head are suppressed, and the clogging of the ejection nozzle and the ejection defect can be suppressed. The content of the polyvalent alcohol is preferably 2 to 20 percent by mass with respect to the total mass of the ink composition. In addition, a solid polyvalent alcohol at 20° C. also has a function similar to that of the polyvalent alcohol used as the organic solvent and may also be used in a manner similar to that described above. As the solid polyvalent alcohol at 20° C., for example, trimethylol propane may be mentioned.
As the glycol ether, for example, an alkylene glycol monoether or an alkylene glycol diether may be mentioned.
As the alkylene glycol monoether, for example, there may be mentioned 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 triglycol), tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol monoethyl ether.
As the alkylene glycol diether, for example, there may be mentioned 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, or dipropylene glycol diethyl ether.
By the addition of the glycol ether to the ink composition, the wettability and the penetration rate to the cloth (such as a polyester cloth) may be adjusted. The content of the glycol ether added to the ink composition is preferably 0.05 to 6 percent by mass with respect to the total mass of the ink composition.
As the organic solvent described above, a plurality of organic solvents may be used in combination. In this case, the content of the total of the organic solvents in the ink composition is, with respect to the total mass of the ink composition, preferably 0.2 to 30 percent by mass, preferably 0.4 to 20 percent by mass, more preferably 0.5 to 15 percent by mass, and further preferably 0.7 to 10 percent by mass. Since the content of the total of the organic solvents is set in the range described above, the suppression of the increase in viscosity of the ink composition, the adjustment of behaviors (penetration and wet spreading) in the cloth, and the reduction in ejection defects of the ink jet head can be performed.

Surfactant

To the ink composition, a surfactant may also be added. The surfactant has a function to decrease the surface tension of the ink composition and to increase the penetration property in a polyester cloth. As the surfactant, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an ampholytic surfactant may be mentioned, and at least one of those surfactants may be used. As the surfactant described above, a surfactant similar to that used for the treatment liquid composition described above may be used.
The content of the surfactant added to the ink composition with respect to the total mass of the ink composition is 0.01 to 3.00 percent by mass, preferably 0.05 to 2.00 percent by mass, more preferably 0.10 to 1.00 percent by mass, and further preferably 0.20 to 0.50 percent by mass. Since the content of the surfactant is set in the range described above, the ejection stability from the ink jet head is secured while foaming is suppressed, and in addition, the ink composition is likely to be brought into contact with the components of the treatment liquid composition adhered to the cloth, so that, for example, the function of the treatment liquid composition to aggregate the ink composition is enhanced.

Chelating Agent

To the ink composition, a chelating agent may also be added. The chelating agent has a function to trap metal ions and the like. Hence, when the chelating agent is used for the ink composition, metals ions contained in the ink composition as impurities or mixed in from a member in contact with the ink composition are trapped, and hence, the generation of foreign materials derived from the metal ions can be reduced. As the chelating agent, for example, there may be mentioned an ethylenediaminetetraacetatic acid (EDTA) salt, a nitrilotriacetate, a hexametaphosphate, a pyrophosphate, or a metaphosphate.

pH Adjuster

To the ink composition, a pH adjuster may also be added. The pH adjuster is not particularly limited, and for example, an organic base or an inorganic base may be mentioned. By the use of at least one of those pH adjusters, the pH of the ink composition is preferably adjusted in a pH range of 7.5 to 10.5. Since the pH of the ink composition is set in the range described above, for example, in an ink jet printing apparatus including an ink jet head, a member, such as an ink repellent film, is suppressed from being corroded.
As the organic base, for example, an alkanolamine, such as triethanolamine, diethanolamine, monoethanolamine, or tri-iso-propanolamine, may be mentioned. In this case, when the pH of the ink composition is set in the range described above by using at least one of those organic bases, a relatively large amount of the pH adjuster is required. In particular, for example, the content thereof with respect to the total mass of the ink composition is approximately 0.1 to 3 percent by mass.
As the inorganic base, for example, a strong base, which is a hydroxide of an alkali metal or an alkaline earth metal, such as lithium hydroxide, potassium hydroxide, or calcium hydroxide, may be used. When the pH of the ink composition is set in the range described above by using at least one of those inorganic bases, for example, the content thereof with respect to the total mass of the ink composition may be set to approximately 0.03 to 0.15 percent by mass. As described above, for example, since the addition amount of the inorganic base is small as compared to that of the organic base, and since the inorganic base has no odor unlike the organic base, the inorganic base is preferably used.

Resin Particles

The ink composition preferably contains resin particles. Since the resin particles are contained, the washing fastness and the abrasion fastness of the printed material are further improved. As the resin particles, a resin emulsion similar to that used for the treatment liquid composition described above may also be used.
The content of the resin particles with respect to the total mass of the ink composition is preferably 2 to 40 percent by mass on a solid component basis, more preferably 4 to 35 percent by mass, and further preferably 5 to 33 percent by mass. Since the content of the resin particles is set in the range described above, the generation of clogging of the nozzle of the ink jet head is reduced, and in addition, the washing fastness and the abrasion fastness of the printed material can be further improved.

Other Components

In the ink composition, as other components, various additives, such as a fungicide, an antiseptic agent, each of which is similar to that used for the treatment liquid, and an antioxidant may also be appropriately used.

Preparation of Ink Composition

The ink composition according to this embodiment may be prepared in such a way that after the components described above are mixed together in an arbitrary order to form a mixture, if needed, impurities and foreign materials are removed by filtration or the like. As a method for mixing the individual components, there may be used a method in which the materials (components) are sequentially charged in a container equipped with a stirring device, such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. As a filtration method, for example, centrifugal filtration or filter filtration may be used.

Physical Properties of Ink Composition

The viscosity of the ink composition at 20° C. is preferably 2 to 15 mPa·s, more preferably 2 to 5 mPa·s, and further preferably 2 to 3.6 mPa·s. Since the viscosity of the ink composition is set in the range described above, the ejection stability and the ejection amount of the ink composition from the ink jet head can be secured. In addition, in the case in which the viscosity of the ink composition is out of the range described above, when the ejection conditions of the ink composition in the ink jet head and/or the type of ink jet head is changed, the ejection stability of the ink composition may be secured in some cases, and for example, under temperature adjustment conditions, the ejection stability may be secured up to a viscosity of 22 mP·s in some cases. The viscosity of the ink composition may be measured by a method similar to that for the treatment liquid composition described above.
The surface tension of the ink composition at 25° C. is set to, for example, preferably 10 to 40 mN/m and more preferably 25 to 40 mN/m. Since the surface tension of the ink composition at 25° C. is set in the range described above, when printing is performed, the wettability to the cloth and the contact with the components of the treatment liquid composition can be promoted. The viscosity and the surface tension of the ink composition each may also be measured by a method similar that for the treatment liquid composition described above.

Printing Apparatus

Printer

Next, a printing apparatus according to this embodiment will be described with reference to FIGURE. The printing apparatus according to this embodiment is preferably an ink jet printing apparatus. The ink jet printing apparatus is an apparatus configured so that by an ink jet method to eject fine liquid droplets of an ink composition, the liquid droplets are landed on a cloth for printing. FIG. 1s a schematic perspective view showing the ink jet printing apparatus according to this embodiment. In this embodiment, as the ink jet printing apparatus, an on-carriage type printer in which ink cartridges are mounted on a carriage will be described by way of example. In addition, in FIGURE, in order to facilitate the recognition of the presence of each member, the scale reduction of the member is made different from that of the actual member.
A printer 1 of this embodiment is a so-called serial printer. The serial printer is a printer configured so that an ink jet head is mounted on a carriage which moves in a predetermined direction, and as the carriage moves, the ink jet head performs printing while moving.
As shown in FIGURE, the printer 1 includes an ink jet head 3, carriage 4, a main scanning mechanism 5, a platen roller 6, and a control portion (not shown) controlling the operation of the entire printer 1. The carriage 4 mounts the ink jet head 3 and also detachably mounts ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f, each of which receives an ink composition to be supplied to the ink jet head 3.
The main scanning mechanism 5 includes a timing belt 8 coupled to the carriage 4, a motor 9 driving the timing belt 8, and a guide shaft 10. The guide shaft 10 functions as a support member of the carriage 4 and is provided in a scanning direction (main scanning direction) of the carriage 4. The carriage 4 is driven by the motor 9 with the timing belt 8 interposed therebetween and is able to reciprocally move along the guide shaft 10. Accordingly, the main scanning mechanism 5 has a function to reciprocally transport the carriage 4 in the main scanning direction.
The platen roller 6 functions to transport a cloth 2 to be printed in a sub-scanning direction (length direction of the cloth 2) orthogonal to the main scanning direction. Hence, the cloth 2 is transported in the sub-scanning direction. In addition, the carriage 4 on which the ink jet head 3 is mounted is able to reciprocally move in the main scanning direction which approximately coincides with the width direction of the cloth 2, and the ink jet head 3 is able to relatively scan the cloth 2 in the main scanning direction and the sub-scanning direction.
The ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f are independent 6 ink cartridges. In the ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f, the ink composition according to this embodiment may be received. In the ink cartridges described above, ink compositions having colors, such as black, cyan, magenta, yellow, white, and orange, are respectively received and can be used in an arbitrary combination. In FIGURE, although the number of the ink cartridges is 6, the number is not limited thereto. On a bottom portion of each of the ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f, a supply port (not shown) is provided to supply the ink composition received in each ink cartridge to the ink jet head 3.
The ink jet head 3 includes a nozzle surface (not shown) in a surface facing the cloth 2. Along the nozzle surface, nozzle lines formed of nozzles (not shown) are separately disposed so as to corresponding to the respective ink compositions. The ink compositions are supplied to the ink jet head 3 from the respective ink cartridges and are ejected in the form of liquid droplets by actuators (not shown) in the ink jet head 3. The liquid droplets of the ink composition thus ejected are landed on the cloth 2 to form an image, a text, a pattern, a color, or the like in a printing region of the cloth 2.
In this case, in the ink jet head 3, as the actuator (driving unit), although a piezoelectric element is used, the actuator is not limited thereto. For example, an electromechanical conversion element which displaces a vibration plate used as the actuator by electrostatic adsorption or an electrothermal conversion element which ejects the ink composition in the form of liquid droplets by foams generated by heating.
In addition, in this embodiment, as the ink jet printing apparatus, although the on-carriage type printer 1 is described by way of example, the ink jet printing apparatus is not limited thereto. For example, an off-carriage type printer in which an ink container, such as an ink cartridge, is not mounted on a carriage may also be used. In addition, the ink jet printing apparatus used in the present disclosure is not limited to the serial printer described above, and there may be used a line head printer in which the ink jet head is formed to have a width equivalent to or large than the width of the cloth 2 and in which printing is performed without moving the ink jet head.

Cloth

As the form of the cloth 2 according to this embodiment, for example, textiles, clothes, or other clothing ornaments may be mentioned. The textiles include a woven fabric, a knitted fabric, a non-woven cloth, and the like. Besides sewn products, such as a T shirt, a handkerchief, a scarf, a towel, a handbag, and a fabric bag, and furniture products, such as a curtain, a sheet, a bedspread, and wallpaper, the clothes and the clothing ornaments also include cloths before and after cutting to be used as components to be sewn. As the form of those products, for example, there may be mentioned a long product wound to have a roll shape, a product cut to have a predetermined size, a product having a product shape.
The cloth 2 is preferably a polyester cloth containing a polyester. Since fibers of the polyester cloth have a lower hydrophilic property than that of cotton, an aqueous pre-treatment agent and/or an aqueous ink composition is liable to be repelled by the polyester fibers and is not likely to be fixed thereto as compared to the case of a cotton cloth. In addition, since the polyester cloth is formed with large (loose) stitches so as to improve the air permeability, the ink composition is more liable to penetrate in the cloth in some cases. Hence, by the polyester cloth, it has been difficult to obtain a preferable chromogenic property; however, according to the treatment liquid composition of the present disclosure, even by the polyester cloth, a preferable chromogenic property can be obtained.
The polyester cloth contains polyester fibers and indicates a cloth formed from, as a forming material, polyester fibers themselves or blend fibers containing polyester fibers and other fibers. As the other fibers, for example, there may be mentioned natural fibers of cotton, silk, hemp, wool, or the like; or synthetic fibers of a polypropylene, an acetate, a triacetate, a polyamide, a polyurethane, a poly(lactic acid), or the like. As the polyester cloth, a cloth formed from, as a forming material, polyester fibers themselves or blend fibers containing a polyester and a cotton is preferable.
The weight per unit area of the cloth 2 is 1.0 to 10.0 ounces, preferably 2.0 to 9.0 ounces, more preferably 3.0 to 8.0 ounces, and further preferably 4.0 to 7.0 ounces. By the treatment liquid according to this embodiment, since the component, such as the cationic compound, of the treatment liquid composition is retained on a surface side of the cloth 2 in the range of the weight per unit area described above, the chromogenic property can be improved as compared to that in the past. In addition, the treatment liquid composition may also be applied to a plurality of clothes having different weights per unit area.
The cloth 2 is preferably a polyester cloth colored with a dye in advance. Since the chromogenic property is improved by the treatment liquid composition according to this embodiment, the substrate color is shielded, and hence, the interference by the substrate color can be suppressed. That is, the treatment liquid composition can be preferably applied to a polyester cloth having a color portion colored in advance. In addition, since the substrate colored in advance is used, a printed material (product) in accordance with the preference of a customer may be provided.
As the cloth colored in advance, a color portion preferably has an L* value of 80 or less. In this case, although the L* value can be measured using a known colorimeter, for example, the measurement may be performed using Spectrolino (available from Gretag Macbeth A.G.). When the ink composition is adhered to a cloth having an L* value of 80 or less, the color of the cloth itself may be observed through an adhesion portion of the ink composition in some cases, and hence, in order to prevent the case described above, the ink composition is required to have a higher chromogenic property (shielding property). Furthermore, in the case of a polyester cloth, as described above, it has been difficult to obtain a preferable chromogenic property.
On the other hand, according to the present disclosure, since the ink composition is preferably allowed to stay on the surface of the cloth by the treatment liquid composition according to the present disclosure, the chromogenic property is improved, and the ink composition can be preferably applied to a cloth having an L* value of 80 or less. The L* value may be 75 or less and may also be 70 or less. According to the treatment liquid composition of the present disclosure, even when a cloth having a deep color as described above is used, the chromogenic property can be improved, and hence, the ink composition can be preferably applied.
As a dye which dyes the cloth 2 in advance, for example, a water-soluble dye, such as an acidic dye or a basic dye, a dispersive dye to be used with a dispersant (surfactant), or a reactive dye may be mentioned. Since the cloth 2 contains polyester fibers, a dispersive dye suitable for dyeing polyester fibers is preferably used. As the dispersive dye suitable for dyeing polyester fibers, a compound which is not likely to be sublimated in a heating step which will be described later is preferable. As the dispersive dye described above, a known dye may be used. In addition, the dispersive dye is preferably used together with a dispersant. As the dispersant, a known dispersant, such as a surfactant, may be used.
As a method to dye the cloth 2 with a dye, in accordance with a material forming the cloth 2 and the form thereof, a known method may be used.

Ink Jet Printing Method

Next, an ink jet printing method according to this embodiment will be described. The ink jet printing method according to this embodiment includes a treatment liquid composition adhesion step in which a treatment liquid composition is adhered to a cloth. In addition, after the treatment liquid composition adhesion step is performed, an ink composition adhesion step is performed such that a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water is adhered to a region to which the treatment liquid composition is adhered.

Treatment Liquid Composition Adhesion Step

In the treatment liquid composition adhesion step, in order to improve the color development of a pigment in a printed material, before the ink composition is adhered to the cloth, a treatment liquid composition which aggregates the components of the ink composition is adhered to the cloth. That is, the cloth 2 is preferably a cloth to which the treatment liquid composition according to this embodiment is adhered.
As the treatment liquid composition to be adhered to the cloth, the treatment liquid composition described above is used. The adhesion amount of the treatment liquid composition is set to, for example, preferably 0.02 to 0.5 g/cm²and more preferably 0.02 to 0.24 g/cm². Since the adhesion amount of the treatment liquid composition is set in the range described above, the treatment liquid composition is likely to be uniformly adhered to the cloth, and aggregate irregularity of an image in the printed material can be suppressed, and hence, the color development can be improved.
In addition, 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 adhered to the cloth is set to preferably 1.6 to 6 μmol/cm²and more preferably 2 to 5 μmol/cm². Since the treatment liquid composition is adhered so that the adhesion amount of the polyvalent metal salt is 1.6 μmol/cm²or more, the chromogenic property of the image in the printed material is improved. In addition, since the treatment liquid composition is adhered so that the adhesion amount of the polyvalent metal salt is 6 μmol/cm²or less, the abrasion fastness of the image is improved.
As a method to adhere the treatment liquid composition to the cloth, for example, a method (dipping coating) in which the cloth is dipped in the treatment liquid composition, a method (roller coating) in which the treatment liquid composition is coated using a roller coater or the like, a method (spray coating) in which the treatment liquid composition is sprayed by a spray device or the like, or a method (ink jet coating) in which the treatment liquid composition is sprayed by an ink jet method may be mentioned, and any one of those methods may be used. Since the treatment liquid composition can be more uniformly adhered to the cloth 2, the treatment liquid composition adhesion step is preferably performed by the ink jet coating. In addition, since the degree of freedom of designing the adhesion amount of the treatment liquid composition is increased, and since the defects generated when the treatment liquid composition is adhered are not likely to occur, the treatment liquid composition is preferably adhered by the roller coating or the spray coating.
The ink jet printing method according to this embodiment may also include, after the treatment liquid composition adhesion step is performed, a treatment liquid composition drying step of drying the treatment liquid composition adhered to the cloth. Although the drying of the treatment liquid composition may be performed by spontaneous drying, in order to increase a drying rate, drying is preferably performed with heating. When the treatment liquid composition drying step is performed with heating, although the heating method thereof is not particularly limited, for example, a heat press method, a normal pressure steam method, a high pressure steam method, or a thermofix method may be mentioned. In addition, as a heat source of the heating, for example, infrared rays (lamp) may be mentioned.
Although a heating temperature in the drying step is not particularly limited, for example, the heating temperature is set to preferably 170° C. or less, more preferably 150° C. or less, and further preferably 130° C. or less. Accordingly, even when the cloth is dyed in advance by a dispersive dye (sublimation dye), the sublimation of the dispersive dye caused by the heat drying is suppressed, and in addition, the degradation in substrate color of the cloth 2 can be suppressed. In addition, the lower limit of the heating temperature is not particularly limited as long as the medium, such as water, contained in the treatment liquid is evaporated and is preferably set to 100° C. or more.
In addition, when the heating temperature is approximately the same as a heating temperature of heating performed after the ink composition is adhered, which will be described later, it is preferable since the drying process can be simplified. In this step, the heating temperature indicates a surface temperature of the treatment liquid composition adhered to the cloth and, for example, may be measured using a non-contact type thermometer IT2-80 (trade name, available from Keyence Corporation). A 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 this embodiment described above is adhered to the cloth in a region to which the treatment liquid composition is adhered. In this step, as the ink composition, the ink composition described above is used. Among the ink compositions, in order to preferably obtain the effect of the present disclosure, a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water is preferable. In addition, in the ink composition adhesion step, a step of adhering a different ink composition may also be performed on the region to which the ink composition described above is adhered. For example, after a white ink composition containing a white pigment is adhered, a color ink composition containing a color pigment may be adhered to a region to which the white ink composition is adhered. When the ink composition adhesion step includes those two steps, dual layer printing in which an image of the color ink composition is formed on an image formed by the white ink composition is recorded. As a method to adhere the ink composition to the cloth, an ink jet method is preferably used.
Since the ink jet printing method according to this embodiment includes the treatment liquid composition adhesion step using the treatment liquid composition described above, the penetration of the ink adhered in the ink composition adhesion step is preferably suppressed, and the ink is allowed to stay on the surface of the cloth. In addition, by a reaction or an interaction between the cationic compound of the treatment liquid composition and the ink components, the ink components are aggregated. Hence, a printed material excellent in chromogenic property can be obtained.
In the ink composition adhesion step, when the ink composition is a white ink composition (white pigment-printing ink jet ink composition) containing a white pigment, the maximum adhesion amount thereof to the cloth is set to preferably 50 to 200 mg/cm², more preferably 80 to 150 mg/cm², and further preferably 90 to 130 mg/cm². When the maximum adhesion amount of the white ink is set as described above, a white chromogenic property is improved, and in particular, when the white ink composition is adhered to a deep color cloth, the color development is improved, and the cloth thus obtained is preferably used as a background image. Since a white image having a preferable color development is provided under a color image, when being formed on a deep color cloth, the color image has a preferable chromogenic property without receiving the influence of the color of the cloth. In addition, when the adhesion amount is set in the range described above, the abrasion fastness of the image is improved, and the aggregate irregularity is preferably not apparent.
On the other hand, in the ink composition adhesion step, when the ink composition is a color ink (color pigment-printing ink jet ink composition), the maximum adhesion amount thereof to the cloth may be set to 1 to 200 mg/cm², and is preferably 1 to 30 mg/cm², more preferably 2 to 25 mg/cm², even more preferably 5 to 20 mg/cm², and particularly preferably 7 to 15 mg/cm². In the case as described above, it is preferable since the chromogenic property of an image to be recorded is improved, the drying property of the image to be recorded is improved, the image is suppressed from being blurred, and images, such as pictures and/or letters, can be reproducibly recorded on the cloth.

Heating Step

In the ink jet printing method according to this embodiment, after the ink composition adhesion step is performed, a step of heating the cloth is preferably performed. By the heating step, the ink composition is likely to uniformly wet spread on the cloth, and in addition, the fixability of the ink composition to the cloth is promoted.
Although a heating method for heating the ink composition applied to the cloth is not particularly limited, for example, a heat press method, a normal pressure steam method, a high pressure steam method, a hot-air drying method, or a thermofix method may be mentioned.
Although not particularly limited, a heating temperature is preferably 100° C. to 200° C. and more preferably 100° C. to 170° C. In addition, when the cloth is formed of cotton, the heating temperature is preferably 120° C. to 160° C., and when the cloth is formed of a polyester or a polyester blend, the heating temperature is more preferably 100° C. to 150° C. Since the heating temperature is in the range described above, the reduction of damage on the cloth and the film formation of the resin particles contained in the ink composition may be promoted.
In addition, although not particularly limited, a heating time may be set, for example, to 30 seconds to 20 minutes and is preferably 2 to 7 minutes and more preferably 3 to 5 minutes. Since the heating time is set in the range described above, while the damage done on the cloth is reduced, the ink can be sufficiently dried. In addition, when the heating temperature described above is approximately the same as the heating temperature of the heating performed after the adhesion of the treatment liquid composition, the drying process can be preferably simplified. In this case, the heating temperature of this step indicates a surface temperature of the treatment liquid composition adhered to the cloth and may be measured, for example, using a non-contact type thermometer IT2-80 (trade name, available from Keyence Corporation).

EXAMPLES

Hereinafter, although the present disclosure will be described in more detail with reference to Examples, the present disclosure is not limited thereto.

Preparation of Treatment Liquid Composition

Compositions of treatment liquid compositions of Examples 1 to 49 and Comparative Examples 1 to 14 are shown in Tables 1 to 7. The unit of the numerical value which represents the content of each component in the table indicates percent by mass and is represented by the rate of the amount of an effective component (solid component). Water is added so that the total mass of the treatment liquid composition is 100 percent by mass. In addition, the column represented by “-” in which the numerical value is not described indicates that no component is contained.

	TABLE 1

	EXAMPLE

	1	2	3	4	5	6	7	8	9	10

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	7.0	7.0	7.0	7.0	5.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—	—	—	—	3.0	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	—	0.6	—	2.5	—	—	—	—	0.6	—
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	1.0	—	5.0	—	1.0	1.0	1.0	1.0	—	1.0
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	—	—	—	—	—	—	—	1.0	—
		OF 1,000 TO 25,000	PITZCOL K-30	—	—	—	—	—	—	—	—	—	1.0
		—	N-VINYL-2-	—	—	—	—	—	—	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	—	—	—	—	—	—	—	—	—	—
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	—	—	—	—	—	—	—	—	—	—
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—	—	—	1.0	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
		BASE

	WATER	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-
		ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES	YES
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	—	—	—	—	—	—	—	—	YES	YES
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	—	—	—	—	—	—	—	—	1.67	1.00

CLOTH	PES	PES	PES	PES	PES	COTTON	PES	PES	PES	PES
					BLEND
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	B′	B′	A	B	B	S	B′	B′	A′	A′
	VISCOSITY	A	A	B	B	A	A	A	A	A	A
	COATING SCAR	A	A	B	A	B	B	A	A	A	A
	STORAGE STABILITY	A	A	A	A	A	A	A	A	A	A
	COATING PROPERTY (SPINNABILITY)	A	B	A	B	A	A	A	A	B	A
	ABRASION FASTNESS	B	B	B	B	B	B	B	B	B	B
	IRREGULARITY OF COLOR	B	B	B	B	B	B	A	A	B	B
	DEVELOPMENT

	TABLE 2

	EXAMPLE

	11	12	13	14	15	16	17	18	19	20

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—	—	—	—	—	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	0.6	—	—	—	—	—	—	—	—	—
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	—	1.0	1.0	1.0	1.0	1.0	0.6	5.0	1.0	1.0
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	1.0	—	—	—	—	—	—	—	—
		OF 1,000 TO 25,000	PITZCOL K-30	1.0	—	0.2	0.5	3.0	5.0	1.0	1.5	1.0	1.0
		—	N-VINYL-2-	—	—	—	—	—	—	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	—	—	—	—	—	—	—	—	—	—
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	—	—	—	—	—	—	—	—	—	—
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—	—	—	—	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
		BASE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES	YES
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES	YES
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	1.67	1.00	0.20	0.50	3.00	5.00	1.67	0.30	1.00	1.00

CLOTH	PES	PES	PES	PES	PES	PES	PES	PES	PES	COTTON
									BLEND
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	A′	A′	B′	B	A′	A′	B′	A	S	S
	VISCOSITY	A	A	A	A	A	A	A	B	A	A
	COATING SCAR	A	A	A	A	A	B	A	B	B	B
	STORAGE STABILITY	A	A	A	A	A	A	A	A	A	A
	COATING PROPERTY (SPINNABILITY)	B	B	A	A	A	A	A	A	A	A
	ABRASION FASTNESS	B	B	B	B	B	B	B	B	A	A
	IRREGULARITY OF COLOR	B	B	B	B	B	B	B	B	B	B
	DEVELOPMENT

	TABLE 3

	EXAMPLE

	21	22	23	24	25	26	27	28	29	30

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	5.0	7.0	7.0	7.0	7.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	3.0	—	—	—	—	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	—	0.6	—	—	0.6	1.0	—	—	—	0.6
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	1.0	—	1.0	1.0	—	—	1.0	1.0	1.0	—
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	1.0	—	—	—	—	—	—	—	—
		OF 1,000 TO 25,000	PITZCOL K-30	1.0	—	1.0	1.0	—	—	—	—	—	—
		—	N-VINYL-2-	—	—	—	—	—	—	1.0	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	—	—	—	—	—	—	—	—	0.1	—
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	0.1	—	0.1
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	1.0	1.0	—	—	1.0	1.0	—	—	—	—
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	1.0	—	—	—	—	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
		BASE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES	YES
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	—	—	—	—	—	—
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	1.00	1.67	1.00	1.00	—	—	—	—	—	—

CLOTH	PES	PES	PES	PES	PES	PES	PES	PES	PES	PES
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	A′	A′	B	B	B′	B	B′	A′	A′	A′
	VISCOSITY	A	A	A	A	A	A	A	A	A	A
	COATING SCAR	A	A	A	A	A	A	A	A	A	A
	STORAGE STABILITY	A	B	A	A	B	B	A	A	A	B
	COATING PROPERTY (SPINNABILITY)	A	B	A	A	B	B	A	A	A	B
	ABRASION FASTNESS	A	A	B	B	A	A	B	B	B	B
	IRREGULARITY OF COLOR	B	B	A	A	B	B	B	C	B	C
	DEVELOPMENT

	TABLE 4

	EXAMPLE

	31	32	33	34	35	36	37	38	39	40

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—	—	—	—	—	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	0.6	—	—	—	—	—	—	—	—	—
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	—	1.0	1.0	1.0	0.6	5.0	1.0	1.0	1.0	1.0
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	—	—	—	—	—	—	—	—	—
		OF 1,000 TO 25,000	PITZCOL K-30	—	—	—	—	—	—	—	—	—	—
		—	N-VINYL-2-	—	—	—	—	—	—	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	0.1	0.01	0.3	0.5	0.1	0.1	0.1	0.1	0.1	0.1
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	—	—	—	—	—	—	—	—	1.0	0.5
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—	—	—	—	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
		BASE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES	YES
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	—	—	—	—	—	—	—	—	—	—
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	—	—	—	—	—	—	—	—	—	—

CLOTH	PES	PES	PES	PES	PES	PES	PES	COTTON	PES	PES
							BLEND
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	B	B	A′	A′	B′	A	S	S	A′	A′
	VISCOSITY	A	A	A	A	A	A	A	A	A	A
	COATING SCAR	A	A	A	A	A	A	A	B	A	A
	STORAGE STABILITY	B	A	A	A	A	B	A	A	A	A
	COATING PROPERTY (SPINNABILITY)	B	A	A	A	A	A	A	A	A	A
	ABRASION FASTNESS	B	B	B	B	B	B	A	A	A	B
	IRREGULARITY OF COLOR	B	B	B	B	B	B	B	B	B	B
	DEVELOPMENT

	TABLE 5

	EXAMPLE

	41	42	43	44	45	46	47	48	49

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	7.0	7.0	5.0	7.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—	—	3.0	—	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	—	—	—	0.6	—	—	—	0.6	—
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	1.0	1.0	1.0	—	1.0	1.0	1.0	—	1.0
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	—	—	—	—	—	—	1.0	—
		OF 1,000 TO 25,000	PITZCOL K-30	—	—	—	—	—	—	1.0	—	1.0
		—	N-VINYL-2-	—	—	—	—	—	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	3.0	0.3	5.0	1.0	—	—	—	—	1.0
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—	1.0	—	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	—	0.1	0.1	0.1	0.1
		BASE

	WATER	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-	BAL-
		ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE	ANCE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	YES	YES	YES	YES	YES
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	—	—	—	—	—	—	YES	YES	YES
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	—	—	—	—	—	—	1.00	1.67	1.00

CLOTH	PES	PES	PES	PES	PES	PES	PES	PES	PES
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	B	A′	B	A′	A′	B	A	A	A
	VISCOSITY	A	A	A	A	A	A	A	A	A
	COATING SCAR	B	A	B	A	A	A	A	A	A
	STORAGE STABILITY	B	A	B	B	A	A	A	B	A
	COATING PROPERTY (SPINNABILITY)	A	A	A	A	A	A	A	B	A
	ABRASION FASTNESS	A	B	A	A	B	B	B	B	A
	IRREGULARITY OF COLOR	B	B	B	B	A	A	B	B	B
	DEVELOPMENT

	TABLE 6

	COMPARATIVE EXAMPLE

	1	2	3	4	5	6	7	8	9	10

TREATMENT	CATIONIC	POLYVALENT METAL	CALCIUM	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0	7.0
LIQUID	COMPOUND	SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—	—	—	—	—	—	—
			SULFATE
	WATER-	MOLECULAR WEIGHT	ALKOX E-45	—	—	—	—	—	—	—	—	—	—
	SOLUBLE	OF 28,000 TO 2,800,000	PITZCOL K-90	0.3	6.0	0.3	6.0	—	—	—	—	—	—
	RESIN	MOLECULAR WEIGHT	ALKOX L-6	—	—	—	—	—	1.0	—	3.0	1.0	3.0
		OF 1,000 TO 25,000	PITZCOL K-30	—	—	1.0	1.0	1.0	—	3.0	—	—	—
		—	N-VINYL-2-	—	—	—	—	—	—	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	—	—	—	—	—	—	—	—	—	—
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—	—	—	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	—	—	—	—	—	—	—	—	1.0	1.0
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—	—	—	—	—	—	—
		BASE
		ACETYLENE GLYCOL	OLFINE E1010	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
		BASE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	YES	YES	—	—	—	—	—	—
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	—	—	YES	YES	YES	YES	YES	YES	YES	YES
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	—	—	3.33	0.17	—	—	—	—	—	—

EVALUATION	CHROMOGENIC PROPERTY	C	S	C	S	C	C	C	C	C	C
	VISCOSITY	S	C	A	C	S	S	S	A	S	A
	COATING SCAR	A	B	A	B	A	A	B	B	A	B
	STORAGE STABILITY	A	A	A	A	A	A	A	A	B	C
	COATING PROPERTY (SPINNABILITY)	A	A	A	A	A	B	A	B	B	B
	ABRASION FASTNESS	B	B	B	B	B	B	B	B	A	A
	IRREGULARITY OF COLOR	A	B	B	B	B	B	B	B	B	B
	DEVELOPMENT

	TABLE 7

	COMPARATIVE EXAMPLE

	11	12	13	14

TREATMENT	CATIONIC	POLYVALENT	CALCIUM	7.0	7.0	7.0	7.0
LIQUID	COMPOUND	METAL SALT	NITRATE
COMPOSITION			TETRAHYDRATE
			MAGNESIUM	—	—	—	—
			SULFATE
	WATER-	MOLECULAR	ALKOX E-45	—	—	—	—
	SOLUBLE	WEIGHT OF 28,000	PITZCOL K-90	0.3	6.0	—	—
	RESIN	TO 2,800,000
		MOLECULAR	ALKOX L-6	—	—	—	1.0
		WEIGHT OF 1,000	PITZCOL K-30	—	—	1.0	—
		TO 25,000
		—	N-VINYL-2-	—	—	—	—
			PYRROLIDONE
	WATER	PARAFFIN WAX	AQUACER497	0.1	0.1	0.1	0.1
	REPELLANT	FLUORINE-BASED	SFCOAT SWK-	—	—	—	—
		WATER REPELLANT	601
	RESIN	VINYL ACETATE-	VINYBLAN	—	—	—	—
	PARTICLES	BASED RESIN	1245L
	SURFACTANT	POLYOXYALKYLENE	EMULGEN 350	—	—	—	—
		BASE
		ACETYLENE	OLFINE E1010	0.1	0.1	0.1	0.1
		GLYCOL BASE

WATER

BALANCE

MOLECULAR WEIGHT	PEAK IN MOLECULAR WEIGHT RANGE	YES	YES	—	—
DISTRIBUTION OF WATER-	OF 28,000 TO 2,800,000 (PEAK A)
SOLUBLE COMPONENT	PEAK IN MOLECULAR WEIGHT RANGE	—	—	YES	YES
	OF 1,000 TO 25,000 (PEAK B)
	PEAK B AREA/PEAK A AREA	—	—	—	—

CLOTH	PES	PES	PES	PES
INK COMPOSITION	INK 1	INK 1	INK 1	INK 1

EVALUATION	CHROMOGENIC PROPERTY	C	S	C	C
	VISCOSITY	S	C	S	S
	COATING SCAR	A	B	A	A
	STORAGE STABILITY	A	C	A	B
	COATING PROPERTY (SPINNABILITY)	A	A	A	B
	ABRASION FASTNESS	B	B	B	B
	IRREGULARITY OF COLOR	B	B	B	B
	DEVELOPMENT

In accordance with the compositions shown in Tables to 7, the treatment liquid compositions of Examples and Comparative Examples were prepared. In particular, after the individual components were charged in a container, mixing and stirring were performed for 2 hours using a magnetic stirrer. Subsequently, filtration was performed using a polytetrafluoroethylene (PTFE)-made membrane filter having a pore size of 5 μm, so that the treatment liquid composition (hereinafter, also referred to as “treatment liquid” in some cases) of each of Examples and Comparative Examples was obtained.
In addition, in Tables 1 to 7, the details of the components not described by the chemical names are as follows. For the components described by their chemical names, the respective chemical reagents were used.
Alkox E-45: trade name, manufactured by Meisei Chemical Works, Ltd., polyethylene oxide
PITZCOL K-90: trade name, manufactured by DKS Co., Ltd., poly(vinyl pyrrolidone)
Alkox L-6: trade name, manufactured by Meisei Chemical Works, Ltd., polyethylene oxide
PITZCOL K-30: trade name, manufactured by DKS Co., Ltd., poly(vinyl pyrrolidone)
AQUACER 497: trade name, manufactured by BYK Japan KK, paraffin wax having 50 percent by mass of a solid component and a melting point of 60° C.
SFCOAT SWK-601: trade name, manufactured by AGC SEIMI CHEMICAL CO., LTD., a fluorine-based water repellant having a melting point of more than 100° C.
Vinyblan 1245L: trade name, manufactured by Nisshin Chemical Industry Co., Ltd., vinyl acetate/acrylic ester having a solid component of 40%
Emulgen 350: trade name, manufactured by Kao Corporation, a polyoxyethylene stearyl ether, the number of carbon atoms of R⁴of the formula (1) being 18, and HLB being 17.8
Olfine E1010: trade name “Olfine E1010”, manufactured by Nisshin Chemical Industry Co., Ltd., acetylene glycol-based surfactant
Water: ion-exchanged water

Molecular Weight Distribution of Water-Soluble Component

After the treatment liquid compositions were each diluted with water to a concentration of 0.1 percent by volume, the measurement was performed under the following conditions using a gel permeation chromatography (GPC). When the maximum peak was observed in a molecular weight range of 28,000 to 2,800,000, in Tables 1 to 7, “yes” is described in the column of “molecular weight range of 28,000 to 2,800,000”. When the maximum peak was observed in a molecular weight range of 1,000 to 25,000, in Tables 1 to 7, “yes” is described in the column of “molecular weight range of 1,000 to 25,000”. In addition, the area ratio of a peak B to a peak A was calculated and was described in the column of “peak B area/peak A area”. In this case, the peak A area indicates the total area of peaks present in the molecular weight range of 28,000 to 2,800,000, and the peak B area indicates the total area of peaks present in the molecular weight range of 1,000 to 25,000.
Apparatus: waters alliance
Columns: G5000PW coupled to G3000PW, manufactured by Tosoh Corporation
Mobile Phase: ultrapure water (for LC-MS), manufactured by Wako Pure Chemical Industries, Ltd.
Flow rate: 1 ml/min
Amount of Sample: 50 μm
Detector: differential refractive index detector
Sample dilution: 0.1% (based on volume)
Filtration before measurement: 0.45-μm filter
Standard Products: poly(ethylene oxide) (calibration curve formed from seven standard products)

Molecular Weight of Water-Soluble Resin

After the water-soluble resins shown in Tables 1 to were each diluted with water to a concentration of 0.1 percent by volume, the measurement was performed in a manner similar to that of the molecular weight distribution of the water-soluble component described above. A water-soluble resin having a primary peak in the molecular weight range of 28,000 to 2,800,000 is categorized in the column of “molecular weight of 28,000 to 2,800,000” in Tables 1 to 7, and a water-soluble resin having a primary peak in the molecular weight range of 1,000 to 25,000 is categorized in the column of “molecular weight of 1,000 to 25,000” in Tables 1 to 7.

Preparation of Ink Composition

The composition of an ink composition (ink 1) used for the evaluation of Examples and Comparative Examples is shown in Table 8. The unit of the numerical value which represents the content of each component in the table is percent by mass and is represented by the rate of the amount of an effective component (solid component). Water was added so that the total mass of the ink composition was 100 percent by mass.

	TABLE 8

	INK COMPOSITION	INK 1

COLORANT	TITANIUM DIOXIDE SLURRY	40.0
RESIN PARTICLES	TAKELAC WS-6021	33.0
ORGANIC SOLVENT	2-PYRROLIDONE	2.0
	GLYCERIN	10.0
	TRIETHYLENE GLYCOL	1.0
	TRIETHYLENE GLYCOL	1.0
	MONOBUTYL ETHER
SURFACTANT	BYK-348	0.3
WATER	ION-EXCHANGED WATER	BALANCE

TOTAL (PERCENT BY MASS)	100.0

In addition, in Table 8, the details of the components not described by the chemical names are as follows. For the components described by the chemical names, the respective chemical reagents were used.
Titanium oxide slurry: NanoTek® Slurry (trade name, manufactured by C.I. Kasei Co., Ltd., titanium oxide solid component: 20 percent by mass, average particle diameter: 250 nm)
Takelac WS-6021: trade name, manufactured by Mitsui Chemicals polyurethane, Inc., solid component: 30 percent by mass, urethane-based resin emulsion
BYK-348: trade name, manufactured by BYK Japan KK, silicone-based surfactant (nonionic surfactant)
Water: ion-exchanged water
After the individual components were charged in a container to form the composition shown in Table 8, and mixing and stirring were then performed for 2 hours using a magnetic stirrer, the mixture thus obtained was sufficiently mixed together by a dispersion treatment using a bead mill in which zirconia beads each having a diameter of 0.3 mm were filled. After stirring was performed for 1 hour, filtration was performed using a PTFE-made membrane filter having a pore size of 5 μm, so that the ink composition was obtained. The numerical value in Table 8 indicates percent by mass, and the purified water (ion-exchanged water) was added so that the total mass of the ink composition was 100 percent by mass.

Formation of Evaluation Cloth

Cloth

In Examples and Comparative Examples, the cloths described in Tables 1 to 7 were used. The details of the cloths described in the tables are as follows.
PES: manufactured by Toms Co., Ltd., glimmer ACTIVE WEAR 3.5 oz (trade name), black, 100% of polyester, dry T shirt, L*=17
Cotton: manufactured by Toms Co., Ltd., Printstar Heavy Weight 5.6 oz (trade name), black, 100% of cotton, T shirt, L*=12
PES Blend: manufactured by American Apparel, the 50/50 (trade name), red, 50% of cotton/50% of PES, T shirt, L*=37

Adhesion of Treatment Liquid Composition

The treatment liquid compositions of Examples and Comparative Examples were adhered to the respective cloths. As an adhesion method, roller coating was used, and the treatment liquid composition was sufficiently impregnated in a sponge roller. Subsequently, the sponge roller was rolled on a front surface of a chest region (one-side surface) of the T shirt used as the cloth four times in a right-to-left direction and a top-to-bottom direction approximately orthogonal thereto, respectively, so that the treatment liquid composition was adhered on the cloth as uniform as possible. In this case, the adhesion amount of the treatment liquid to the cloth was 20 g per A4 size area.
Next, as a drying step, on the cloth to which the treatment liquid composition was adhered, heat drying was performed at 130° C. for 90 seconds by a pressing force of 3.0 kN using a heat press machine. Through the drying step, an evaluation cloth treated by the treatment liquid composition was obtained.

Pigment Printing

Next, by an ink jet method using an ink jet printer SC-F200 (trade name, available from Seiko Epson Corporation), solid printing was performed by the ink composition on a region to which the treatment liquid composition was adhered. In this case, the adhesion amount of the ink composition to the cloth was set to 300 g/m².
Subsequently, as the heating step, heat drying was performed at 130° C. for 60 seconds by a pressing force of 3.0 kN using a heat press machine. After the heating step was performed, an evaluation cloth (printed material) on which printing was performed by the ink composition was obtained.

Evaluation Test

The treatment liquid compositions, the evaluation cloths to each of which the treatment was performed by the treatment liquid composition, and the evaluation cloths to each of which the ink composition was printed were evaluated as described below, and the results thereof are shown in Tables 1 to 7.

Chromogenic Property

As the index of the chromogenic property of the white pigment (degree of white), at a region α of the evaluation cloth to which the ink composition was adhered, color measurement was performed. In particular, by the use of a colorimeter Spectrolino (available from Gretag Macbeth A.G.), the L* value was measured and then evaluated in accordance with the following criteria. When the chromogenic property was ranked as B′ or more, it was evaluated that the effect of the present disclosure could be obtained.
S: L* value is 90 or more.
A: L* value is 85 to less than 90.
A′: L* value is 80 to less than 85.
B: L* value is 78 to less than 80.
B′: L* value is 76 to less than 78.
C: L* value is 74 to less than 76.

Viscosity

The viscosity of the treatment liquid composition immediately after the preparation thereof was measured at 20° C. using a viscoelastic tester MCR-301 (manufactured by Anton Paar) in such a way that the shear rate was increased from 0.01 to 1.00 s⁻¹, and the viscosity was read at a shear rate of 0.10 s⁻¹. When the evaluation result of the viscosity was B or more, it was evaluated that the effect of the present disclosure could be obtained.
S: Viscosity is 1 to less than 5 mPa·s.
A: Viscosity is 5 to less than 30 mPa·s.
B: Viscosity is 30 to less than 100 mPa·s.
C: Viscosity is 100 mPa·s or more.

Coating Scar

Evaluation of a coating scar of the evaluation cloth treated with the treatment liquid composition was performed. When the treatment liquid composition is adhered to the cloth which is colored, in comparison with a portion of the cloth to which the treatment liquid composition is not adhered, the difference in appearance, such as the change in hue, may be generated as the coating scar in some cases. In this evaluation, a region β to which the treatment liquid composition was not adhered and a region γ to which the treatment liquid composition was adhered were observed by visual inspection, and the evaluation was performed in accordance with the following criteria.
A: The difference in appearance between the region β and the region γ is hardly observed.
B: The difference in appearance between the region β and the region γ is apparently observed.

Storage Stability

After the treatment liquid composition was prepared, the treatment liquid composition was left at room temperature for 7 days, and it was evaluated whether a solid material was separated or not by precipitation or floatation.
A: No separation of solid material occurs.
B: Separation of solid material occurs.

Coating Property (Spinnability)

When the treatment liquid composition was applied to the cloth by roller coating, the coating property was evaluated in accordance with the following criteria.
A: Droplets are neither generated nor scattered.
B: Droplets are generated and scattered.

Abrasion Fastness

After the evaluation cloth to which the ink composition was printed was washed with water and then sufficiently dried, by using a Gakushin-type abrasion fastness tester AB-301S manufactured by Tester Sangyo Co., Ltd., an abrasion fastness test was performed by rubbing the cloth 150 times with a load of 200 g. Evaluation was based on the level of dry test performed in accordance with Japanese Industrial Standards (JIS) JIS L0849 which confirms the degree of peeling of the ink composition.
A: Level 3 or more
B: less than Level 3

Irregularity of Color Development

By the use of the evaluation cloth to which the ink composition was printed, irregularity of color development of the pigment was evaluated by visual inspection.
A: No granular irregularity of color is observed.
B: Although granular irregularity of color is observed, the level thereof is in an acceptable range.
C: Granular irregularity of color is observed, and the level thereof is not acceptable.
As shown in Tables 1 to 7, according to Examples 1 to 49, it is found that the viscosity of the treatment liquid composition is preferable, and a printed material excellent in chromogenic property can be obtained. In addition, the results of the coating scar, the storage stability, the coating property, and the abrasion fastness are excellent. Furthermore, except for Examples 28 and 30, it is shown that the irregularity of color development is suppressed. On the other hand, according to Comparative Examples 1 to 14, it is found that at least one of the viscosity and the chromogenic property is inferior.

Operation and Effect

Hereinafter, the results derived from this embodiment will be described.
The treatment liquid composition is a treatment liquid composition which is used to be adhered to a cloth and which contains a cationic compound, a water-soluble resin, and water; the molecular weight distribution of a water-soluble component contained in the treatment liquid composition has a maximum peak in a molecular weight range of 28,000 to 2,800,000; and the content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to the total mass of the treatment liquid composition.
According to this structure, a treatment liquid composition which preferably maintains its viscosity low and which is able to obtain a printed material excellent in chromogenic property can be obtained. The reason for this is that since the treatment liquid composition contains the water-soluble resin, the molecular weight distribution of the water-soluble component has a maximum peak in a large molecular weight region of 28,000 to 2,800,000, and the content of the water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 percent by mass or more with respect to the total mass of the treatment liquid composition, the viscosity of an ink composition is increased, the fluidity of the ink composition is degraded, and hence, the ink composition is allowed to easily stay on the surface of the cloth.
In more particular, the reason described above will be described in more detail. When the ink composition is adhered to the cloth to which the treatment liquid composition is adhered in advance, in the ink composition, the water-soluble resin is partially dissolved. According to the water-soluble component in the treatment liquid composition represented by the water-soluble resin, since the molecular weight distribution thereof has a maximum peak in a relatively large molecular weight range of 28,000 to 2,800,000, when the water-soluble resin is dissolved in the ink composition, the viscosity thereof is increased. Because of the increase in viscosity, the fluidity of the ink composition is degraded, and the ink composition is not likely to penetrate in the cloth and is likely to stay on the surface of the cloth.
In addition, besides the water-soluble resin, since the cationic compound is also contained in the treatment liquid composition, the cationic compound functions to promote the aggregation of the components in the ink composition. By the increase in viscosity and the aggregation described above, the ink composition is likely to stay on the surface of the cloth, and hence, a preferable color development can be obtained. In addition, since the content of the water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 5 percent by mass or less with respect to the total mass of the treatment liquid composition, the viscosity of the treatment liquid composition is preferably not excessively increased.
In the treatment liquid composition described above, the molecular weight distribution of the water-soluble component preferably further has a maximum peak in a molecular weight range of 1,000 to 25,000, and the peak area of a molecular weight range of 28,000 to U.S. Pat. No. 2,800,000 to the peak area of a molecular weight range of 1,000 to 25,000 is preferably 1:5 to 5:1.
According to this structure, since the treatment liquid composition further contains a water-soluble component having a relatively small molecular weight, the chromogenic property is further improved. The reason for this is believed that the rate of dissolution of the water-soluble component having a relatively small molecular weight in the ink composition is faster than that of a water-soluble component having a large molecular weight. Since the rate of dissolution in the ink composition is high, immediately after the adhesion of the ink composition, the viscosity of the ink composition tends to be increased, and the ink composition is likely to stay on the surface of the cloth, so that the chromogenic property can be improved.
In the treatment liquid composition, the water-soluble resin is preferably at least one of a poly(ethylene oxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and a poly(vinyl pyrrolidone).
According to the structure described above, the water-soluble resin is more likely to be dissolved in the ink composition, and the viscosity of the ink composition is likely to be increased. Hence, the ink composition is likely to stay on the surface of the cloth, and the chromogenic property can be improved. In addition, in particular, a poly(vinyl pyrrolidone) has a preferable solubility and a low spinnability and tends to improve the coating property.
The treatment liquid composition described above further preferably contains a water repellant, and the content of the water repellant with respect to the total mass of the treatment liquid composition is preferably 0.01 to 0.30 percent by mass.
According to the structure described above, since a hydrophobic property is imparted to the surface of the cloth to which the treatment liquid composition is adhered, the ink composition is more likely to stay on the surface of the cloth, and hence, the chromogenic property can be improved.
In the treatment liquid composition described above, the water repellant is preferably at least one selected from a fluorine-based water repellant, a silicone-based water repellant, and a paraffin wax.
According to the structure described above, the hydrophobic property is preferably imparted to the surface of the cloth, the ink composition is more likely to stay on the surface of the cloth, and hence, the chromogenic property can be improved.
In the treatment liquid composition described above, the water repellant is preferably a resin having a melting point of 100° C. or less.
According to the structure described above, the coating property of the treatment liquid composition is improved. The treatment liquid composition can be uniformly adhered, and hence, the irregularity of color development can be suppressed.
In the treatment liquid composition described above, the cloth is preferably a polyester or a blend containing a polyester and a cotton.
According to the structure described above, for example, by the polyester or the blend containing a polyester and a cotton, which has a low hydrophilic property as compared to that of cotton, a preferable chromogenic property can be obtained.
In the treatment liquid composition described above, the cloth is preferably a cloth having a color portion, and the L* value of the color portion is preferably 80 or less.
According to the structure described above, in the cloth which is deeply colored, the color (substrate color) of the cloth functioning as an underlayer is shielded, and the influence of the substrate color is not likely to be received. Hence, a preferable chromogenic property can be obtained.
The treatment liquid composition described above preferably further contains resin particles.
According to the structure described above, the fixability of the colorant contained in the ink composition is improved. Hence, for example, the washing fastness and the abrasion fastness of the ink composition thus adhered can be improved.
The treatment liquid composition described above preferably further contains a nonionic surfactant, and the nonionic surfactant is preferably a polyoxyethylene oleyl ether.
According to the structure described above, the wet spreadability of the ink composition can be improved, and the granularity of an image recorded by the ink composition can be suppressed.
In the treatment liquid composition described above, the cationic compound is preferably a polyvalent metal salt, and the polyvalent metal salt is preferably at least one selected from calcium nitrate, calcium chloride, and magnesium sulfate.
According to the structure described above, the aggregation of the components in the ink composition is preferably promoted, and a preferable chromogenic property can be obtained.
The treatment liquid composition described above is preferably used for ink jet pigment printing.
According to the structure described above, in the ink jet pigment printing, a preferable chromogenic property can be obtained.
A set is a set including the treatment liquid composition described above and a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water.
According to the structure described above, by the treatment liquid composition, the chromogenic property of the pigment-printing ink jet ink composition can be improved.
In the set described above, the pigment-printing ink jet ink composition is preferably a white ink containing a white pigment.
According to the structure described above, the chromogenic property of the white ink can be improved.
An ink jet printing method is an ink jet printing method which includes a treatment liquid composition adhesion step of adhering the treatment liquid composition described above to the cloth.
According to the structure described above, by the treatment liquid composition, the chromogenic property of the ink jet ink composition can be improved.
The ink jet printing method described above preferably further includes, after the treatment liquid composition adhesion step is performed, an ink composition adhesion step of adhering a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water to a region to which the treatment liquid composition is adhered.
According to the structure described above, by the treatment liquid composition, the chromogenic property of the pigment-printing ink jet ink composition can be improved.
The cloth is a cloth to which the treatment liquid composition described above is adhered.
According to the structure described above, when the ink composition is adhered, a cloth capable of improving the chromogenic property thereof can be obtained.
The entire disclosure of Japanese Patent Application No. 2018-143267, filed Jul. 31, 2018 is expressly incorporated by reference herein.

Claims

What is claimed is:

1. A treatment liquid composition which is used to be adhered to a cloth, the treatment liquid composition comprising: 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 peak in a molecular weight range of 28,000 to 2,800,000, and

a content of a water-soluble resin having a molecular weight of 28,000 to 2,800,000 is 0.6 to 5.0 percent by mass with respect to a total mass of the treatment liquid composition.

2. The treatment liquid composition according to claim 1, wherein

the molecular weight distribution of the water-soluble component further has a maximum peak in a molecular weight range of 1,000 to 25,000, and

a ratio of a peak area of a molecular weight of 28,000 to 2,800,000 to a peak area of a molecular weight of 1,000 to 25,000 is 1:5 to 5:1.

3. The treatment liquid composition according to claim 1, wherein

the water-soluble resin is at least one selected from a poly(ethylene oxide), a carboxymethyl cellulose, a hydroxyethyl cellulose, and a poly(vinyl pyrrolidone).

4. The treatment liquid composition according to claim 1,

further comprising a water repellant, wherein

a content of the water repellant is 0.01 to 0.30 percent by mass with respect to the total mass of the treatment liquid composition.

5. The treatment liquid composition according to claim 4, wherein

the water repellant is at least one selected from a fluorine-based water repellant, a silicone-based water repellant, and a paraffin wax.

6. The treatment liquid composition according to claim 4, wherein

the water repellant is a resin having a melting point of 100° C. or less.

7. The treatment liquid composition according to claim 1, wherein

the cloth is a polyester or a blend containing a polyester and a cotton.

8. The treatment liquid composition according to claim 1, wherein

the cloth has a color portion, and an L* value of the color portion is 80 or less.

9. The treatment liquid composition according to claim 1,

further comprising resin particles.

10. The treatment liquid composition according to claim 1,

further comprising a nonionic surfactant, wherein

the nonionic surfactant is a polyoxyethylene oleyl ether.

11. The treatment liquid composition according to claim 1, wherein

the cationic compound is a polyvalent metal salt, and

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

12. The treatment liquid composition according to claim 1, wherein

the treatment liquid composition is used for ink jet pigment printing.

13. A set comprising:

the treatment liquid composition according to claim 1; and

a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water.

14. The set according to claim 13, wherein

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

15. An ink jet printing method comprising:

adhering the treatment liquid composition according to claim 1 to the cloth.

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

further comprising, after the adhering the treatment liquid composition is performed, adhering a pigment-printing ink jet ink composition which contains a pigment, resin particles, and water to a region to which the treatment liquid composition is adhered.

17. A cloth to which the treatment liquid composition according to claim 1 is adhered.