Colored paste composition, printed fabric, and method for producing deinked printed fabric

Abstract

A color paste composition containing a pigment and a deinkable adhesive, the deinkable adhesive having a weight average molecular weight (Mw) of 100,000 or less.

Description

Technical Field

[0001] The present invention relates to a color paste composition, a resist-dyed fabric, and a method for producing a deinked resist-dyed fabric. This application claims priority based on Japanese Patent Application No. 2023-217972 filed in Japan on December 25, 2023, and incorporates its content herein.

Background Art

[0002] A vertical rectangular cloth tied to a pole, a promotional flag, is installed at the storefronts of various industries mainly at restaurants as a promotional tool. The promotional flag is printed with a color paste composition.

[0003] As a color paste composition, Patent Document 1 discloses a pigment resist dye containing a polymer (A) obtained by polymerizing a polymerizable monomer containing a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having a hydrolyzable silyl group, and titanium oxide (B). The pigment resist dye is characterized in that the elongation rate of the film of the polymer (A) alone is in the range of 1,200 to 5,000%, and the 1,000% modulus is 0.1 MPa or more. According to the pigment resist dye, even when it contains titanium oxide as a pigment and is printed on a fabric, the original texture of the fabric is not impaired, and the printed portion has excellent washing resistance, rubbing resistance, etc., and further excellent washing resistance in the dye overdyed portion. It is disclosed that a printed fabric with a natural texture and suppressed color fading during washing etc. can be obtained.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Advertising flags are typically used for only half a month to six months, resulting in a high turnover rate and large amounts of waste. In recent years, environmental considerations have become more important, and the recycling of advertising flags is desired. Therefore, from the perspective of advertising flag recycling, it is preferable that the colored adhesive composition has excellent deinking properties. However, conventional colored paste compositions, such as those described in Patent Document 1, primarily focus on maintaining colorfastness against friction during wear and washing, and prioritize adhesion to fibers. Therefore, there is room for improvement in the deinking properties of the colored paste compositions.

[0006] The present invention has been made in view of these circumstances, and aims to provide a colored paste composition that has good washability and abrasion resistance as well as good deinking properties, a printed fabric printed with the colored paste composition, and a method for producing a deinked printed fabric obtained by deinking the printed fabric. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A colored paste composition comprising a pigment and a deinking agent, wherein the weight-average molecular weight (Mw) of the deinking agent is 100,000 or less. [2] The colored paste composition according to [1], wherein the acid value of the deinking adhesive is 8 mg KOH / g or more and 45 mg KOH / g or less. [3] The colored paste composition according to [1] or [2], wherein the content of the deinking agent is 1.0% by mass or more and 20.0% by mass or less with respect to the total amount of the colored paste composition. [4] A colored paste composition according to any one of [1] to [3], further comprising a crosslinking agent. A printed cloth, which has been printed with any one of the colored paste compositions described in [5][1] to [4]. A method for producing a deinked printed fabric, comprising a deinking step of mixing the printed fabric described in [6][5], a deinking agent, and a contact body, and applying an external force by bringing the contact body into contact with the printed fabric to obtain a deinked printed fabric. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a colored paste composition that has good washability and abrasion resistance as well as good deinking properties, a printed fabric printed with the colored paste composition, and a method for producing a deinked printed fabric obtained by deinking the printed fabric. [Modes for carrying out the invention]

[0009] (Colored paste composition) The colored adhesive composition of this embodiment contains a pigment and a deinking binder.

[0010] <Pigments> Pigments are powders used for coloring that are insoluble in water and oil. The pigment may be a pigment dispersion. The pigment content in the pigment dispersion is preferably 20-60% by mass, preferably 25-50% by mass, and preferably 30-45% by mass. The pigment may be a surface-treated pigment.

[0011] The pigment may be an inorganic pigment or an organic pigment. Examples of inorganic pigments include metal oxide pigments such as titanium dioxide, zinc oxide, iron oxide, iron black, and chromium oxide; metal composite oxide pigments such as titanium yellow, zinc-iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, and copper-iron black; chromic acid pigments such as lead yellow and molybdenum orange; ferrocyanide pigments such as Prussian blue; sulfide pigments such as cadmium yellow, cadmium red, zinc sulfide, and barium sulfide; and ultramarine, calcium carbonate, cobalt violet, yellow iron oxide, and carbon black.

[0012] Examples of organic pigments include azo pigments such as lake red, permanent red, brilliant carmine, calcium lake, naphthol AS red, benzimidazolone yellow, disazo yellow HR, pyrazolone red, condensed azo yellow, condensed azo red, condensed azo brown, and nickel azo yellow; phthalocyanine pigments such as phthalocyanine blue, chlorinated phthalocyanine green, and brominated phthalocyanine green; and condensed polycyclic pigments such as anthraquinone yellow, dianthaquinonyl red, indanthrene blue, thioindigobordeaux, perinone orange, perylene scarlet, perylene orange, perylene red, perylene maroon, quinacridone red, quinacridone magenta, quinacridone scarlet, dioxazine violet, isoindolinone yellow, quinophthalone yellow, isoindoline yellow, and diketopyrrolopyrrole red.

[0013] Examples of commercially available pigment dispersions include aqueous pigment dispersions such as DEXCEL BLACK HR CONC (manufactured by DIC Corporation), DEXCEL BLUE HR (manufactured by DIC Corporation), DEXCEL RED HBH (manufactured by DIC Corporation), and DEXCEL LIGHT YELLOW HG (manufactured by DIC Corporation).

[0014] Pigments and pigment dispersions may be used individually or in combination of two or more types. The pigment dispersion content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, particularly preferably 5% by mass or more, and most preferably 8% by mass or more, based on the total amount of the colored adhesive composition of this embodiment. The pigment dispersion content is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less, based on the total amount of the colored adhesive composition of this embodiment. Furthermore, the pigment dispersion content may be 7% by mass or less, or 5% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment.

[0015] If the content of the pigment dispersion is at least the above-mentioned preferable lower limit value, the wash resistance and rubbing fastness are further improved. If the content of the pigment dispersion is at most the above-mentioned preferable upper limit value, the deinking property is further improved.

[0016] For example, the content of the pigment dispersion is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, and still more preferably 8% by mass or more and 12% by mass or less, based on the total amount of the color paste composition of the present embodiment. Also, the content of the pigment dispersion may be 1% by mass or more and 7% by mass or less, or may be 1% by mass or more and 5% by mass or less, based on the total amount of the color paste composition of the present embodiment.

[0017] The content of the pigment is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.2% by mass or more, even more preferably 0.6% by mass or more, particularly preferably 1% by mass or more, and most preferably 1.6% by mass or more, based on the total amount of the color paste composition of the present embodiment. The content of the pigment is preferably 12% by mass or less, more preferably 9% by mass or less, still more preferably 7.2% by mass or less, and particularly preferably 6% by mass or less, based on the total amount of the color paste composition of the present embodiment. Also, the content of the pigment may be 4.2% by mass or less, or may be 3% by mass or less, based on the total amount of the color paste composition of the present embodiment.

[0018] If the content of the pigment is at least the above-mentioned preferable lower limit value, the wash resistance and rubbing fastness are further improved. If the content of the pigment is at most the above-mentioned preferable upper limit value, the deinking property is further improved.

[0019] For example, the content of the pigment is preferably 0.2% by mass or more and 12% by mass or less, more preferably 1% by mass or more and 9% by mass or less, and still more preferably 1.6% by mass or more and 7.2% by mass or less, based on the total amount of the color paste composition of the present embodiment. Also, the content of the pigment may be 0.2% by mass or more and 4.2% by mass or less, or may be 0.2% by mass or more and 3% by mass or less, based on the total amount of the color paste composition of the present embodiment.

[0020] <Deinking adhesive> Deinking agents are components that enhance the fixation of pigments in color paste compositions to printed fabrics, and are easily washed away during the deinking process. Furthermore, the deinking adhesive is a resin with a weight-average molecular weight (Mw) of 100,000 or less. The deinking adhesive is preferably an aqueous dispersion of a resin with a weight-average molecular weight (Mw) of 100,000 or less. The solid content of the deinking adhesive is preferably 10 to 55% by mass, preferably 15 to 50% by mass, and preferably 20 to 45% by mass. The weight-average molecular weight (Mw) of the deinking adhesive is 100,000 or less, preferably 80,000 or less, more preferably 75,000 or less, and even more preferably 50,000 or less. The weight-average molecular weight (Mw) of the deinking adhesive is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 16,000 or more.

[0021] If the weight-average molecular weight (Mw) of the deinking agent is 100,000 or less, the deinking properties of the colored paste composition of this embodiment are improved. Furthermore, if the weight-average molecular weight (Mw) of the deinking agent is below the above preferred upper limit, the deinking properties are further improved. When the weight-average molecular weight (Mw) of the deinking adhesive is above the above preferred lower limit, the washability and abrasion resistance are further improved.

[0022] The weight-average molecular weight (Mw) of the deinking adhesive is preferably, for example, 10,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 14,000 to 75,000, and particularly preferably 16,000 to 50,000.

[0023] In this specification, the weight-average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

[0024] The acid value of the deinking adhesive is preferably 8 mg KOH / g or higher, more preferably 15 mg KOH / g or higher, and even more preferably 20 mg KOH / g or higher. The acid value of the deinking adhesive is preferably 45 mg KOH / g or less, more preferably 40 mg KOH / g or less, and even more preferably 30 mg KOH / g or less.

[0025] If the acid value of the deinking adhesive is above the preferred lower limit mentioned above, the washability and abrasion resistance will be further improved. If the acid value of the deinking adhesive is below the above preferred upper limit, the deinking properties will be further improved.

[0026] For example, the acid value of the deinking adhesive is preferably 8 mg KOH / g or more and 45 mg KOH / g or less, more preferably 15 mg KOH / g or more and 40 mg KOH / g or less, and even more preferably 20 mg KOH / g or more and 30 mg KOH / g or less.

[0027] In this specification, the acid value is the value obtained by converting the amount of acid in 1 g of resin, calculated by titrating the acid with an alkali, into the number of mg of potassium hydroxide, in accordance with JIS K 0070:1992.

[0028] From the viewpoint of storage stability, the pH of the deinking adhesive is preferably 4 to 11, preferably 5 to 10, and preferably 6 to 10.

[0029] In this specification, pH refers to the value measured at 25°C using a pH meter (Horiba, Ltd.: pH meter F-71).

[0030] From the viewpoint of the texture of the fibers, urethane resin or acrylic resin is preferred as a deinking adhesive.

[0031] ≪Urethane resin≫ The urethane resin preferably has structural units derived from polyol compounds, structural units derived from isocyanate compounds, and structural units derived from hydroxycarboxylic acid compounds.

[0032] Specific examples of constituent units derived from polyol compounds include those derived from terephthalic acid, isophthalic acid, ethylene glycol, and diethylene glycol.

[0033] Specific examples of constituent units derived from isocyanate compounds include those derived from isophorone diisocyanate. Specific examples of constituent units derived from hydroxycarboxylic acid compounds include those derived from 2,2'-dimethylolpropionic acid and 2,2'-dimethylolbutanoic acid.

[0034] The weight-average molecular weight (Mw) of the urethane resin is 100,000 or less, preferably 80,000 or less, more preferably 75,000 or less, and even more preferably 65,000 or less. The weight-average molecular weight (Mw) of the urethane resin is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.

[0035] When the weight-average molecular weight (Mw) of the urethane resin is 100,000 or less, the deinking properties of the colored adhesive composition of this embodiment are improved. Furthermore, when the weight-average molecular weight (Mw) of the urethane resin is below the above-mentioned preferred upper limit, the deinking properties are further improved. When the weight-average molecular weight (Mw) of the urethane resin is above the above preferred lower limit, the washability and abrasion resistance are further improved.

[0036] The weight-average molecular weight (Mw) of the urethane resin is preferably, for example, 10,000 to 100,000, more preferably 10,000 to 80,000, even more preferably 20,000 to 75,000, and particularly preferably 30,000 to 65,000.

[0037] The weight-average molecular weight (Mw) of urethane resin refers to the value measured under the following conditions. Measurement device: High-speed GPC device (HLC-8220GPC manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. TSKgelG5000(7.8mml.D.×30cm)×1 piece TSKgel G4000 (7.8mm l.D. x 30cm) x 1 TSKgel G3000 (7.8mm l.D. x 30cm) x 1 TSKgel G2000 (7.8mm l.D. x 30cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40℃ Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard samples: A calibration curve will be created using the monodisperse polystyrene listed below. (Monodisperse polystyrene) TSKgel Standard Polystyrene A-500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-1000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-2500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-5000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-1, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-2, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-4, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-10, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-20, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-40, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-80, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-128, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-288, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-550, manufactured by Tosoh Corporation.

[0038] ≪Acrylic resin≫ The acrylic resin is preferably a styrene-acrylic resin. The styrene-acrylic resin preferably has constituent units derived from styrene, constituent units derived from acrylic acid esters, and constituent units derived from acrylic acid, methacrylic acid, and / or acrylamide. Furthermore, it is preferable that the styrene-acrylic resin has constituent units derived from methacrylic acid.

[0039] Examples of acrylic acid esters include ethyl acrylate and n-butyl acrylate. Examples of acrylamides include N-methylolacrylamide.

[0040] The weight-average molecular weight (Mw) of the acrylic resin is 100,000 or less, preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 29,500 or less. The weight-average molecular weight (Mw) of the acrylic resin is preferably 10,000 or more, more preferably 14,000 or more, and even more preferably 16,000 or more.

[0041] When the weight-average molecular weight (Mw) of the acrylic resin is 100,000 or less, the deinking properties of the colored adhesive composition of this embodiment are improved. Furthermore, when the weight-average molecular weight (Mw) of the acrylic resin is below the above-mentioned preferred upper limit, the deinking properties are further improved. When the weight-average molecular weight (Mw) of the acrylic resin is above the preferred lower limit mentioned above, the washability and abrasion resistance are further improved.

[0042] The weight-average molecular weight (Mw) of the acrylic resin is preferably, for example, 10,000 to 100,000, more preferably 10,000 to 50,000, even more preferably 14,000 to 40,000, and particularly preferably 16,000 to 29,500.

[0043] The weight-average molecular weight (Mw) of acrylic resin refers to the value measured under the following conditions. If the acrylic resin is difficult or impossible to dissolve, and it is not possible to prepare a 10 mM LiBr DMF solution with a sample concentration of 0.4 mass%, the weight-average molecular weight (Mw) is considered unmeasurable and is assumed to be greater than 100,000. Measurement device: High-speed GPC device (HLC-8420GPC manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. TSKgel-SuperAWN-H x 1 bottle Detector: RI (Differential Refractometer) Column temperature: 40℃ Eluent: 10mM LiBr DMF Flow rate: 0.6mL / min Injection volume: 30 μL (10 mM LiBr DMF solution with a sample concentration of 0.4% by mass) Standard samples: A calibration curve will be created using the monodisperse polystyrene listed below. (Monodisperse polystyrene) TSKgel Standard Polystyrene A-500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-1000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-2500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-5000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-1, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-2, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-4, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-10, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-20, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-40, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-80, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-128, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-288, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-550, manufactured by Tosoh Corporation.

[0044] Deinking adhesives may be used individually or in combination of two or more types. The content of the deinking adhesive as solids is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more, relative to the total amount of the colored adhesive composition of this embodiment. Furthermore, the content of the deinking adhesive as solid matter may be 1.5% by mass or more, or 2% by mass or more, relative to the total amount of the colored adhesive composition of this embodiment. The content of the deinking adhesive as solids is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 4% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment. Furthermore, the amount of the deinking adhesive as solid content may be 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less, relative to the total amount of the colored paste composition of this embodiment.

[0045] If the content of the deinking adhesive is above the preferred lower limit mentioned above, the wash resistance and abrasion resistance will be further improved. If the content of the deinking adhesive is below the above preferred upper limit, the deinking properties will be further improved.

[0046] For example, the content of the deinking adhesive as solids is preferably 0.1% to 10% by mass, more preferably 0.3% to 5% by mass, even more preferably 0.5% to 4% by mass, and particularly preferably 1% to 4% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0047] When the deinking adhesive is an aqueous dispersion of urethane resin, the solid content (urethane resin) of the deinking adhesive is preferably 0.1% to 10% by mass, more preferably 0.3% to 5% by mass, even more preferably 0.5% to 4% by mass, and particularly preferably 1% to 4% by mass, based on the total amount of the color adhesive composition of this embodiment. When the deinking adhesive is an aqueous dispersion of acrylic resin, the solid content (acrylic resin) of the deinking adhesive is preferably 0.1% to 10% by mass, more preferably 0.3% to 5% by mass, even more preferably 0.5% to 4% by mass, and particularly preferably 1% to 4% by mass, based on the total amount of the color adhesive composition of this embodiment.

[0048] The mass ratio of the solid content of the deinkable adhesive made of urethane resin to the solid content of the deinkable adhesive made of acrylic resin [solid content of urethane resin deinkable adhesive / solid content of acrylic resin deinkable adhesive] is preferably 0.10 / 1 to 3.00 / 1, preferably 0.20 / 1 to 2.50 / 1, preferably 0.30 / 1 to 2.00 / 1, and preferably 0.50 / 1 to 1.50 / 1.

[0049] <Optional ingredients> The colored adhesive composition of this embodiment may contain optional components. Optional components include binder resins, crosslinking agents, organic solvents, viscosity modifiers, thickeners, pH adjusters, wetting agents, humectants, flame retardants, and water.

[0050] ≪Binder Resin≫ The colored adhesive composition of this embodiment preferably contains a binder resin. Binder resins are resins with a weight-average molecular weight (Mw) exceeding 100,000. The binder resin is preferably an acrylic resin emulsion. The solid content of the binder resin is preferably 10 to 55% by mass, preferably 15 to 50% by mass, and preferably 20 to 45% by mass.

[0051] The acid value of the binder resin is preferably 8 mg KOH / g or higher, and more preferably 15 mg KOH / g or higher. The acid value of the binder resin is preferably 45 mg KOH / g or less, more preferably 40 mg KOH / g or less, and even more preferably 30 mg KOH / g or less.

[0052] If the acid value of the binder resin is above the preferred lower limit mentioned above, the washability and abrasion resistance will be further improved. If the acid value of the binder resin is below the above preferred upper limit, the deinking properties will be further improved.

[0053] For example, the acid value of the binder resin is preferably 8 mg KOH / g or more and 45 mg KOH / g or less, more preferably 15 mg KOH / g or more and 40 mg KOH / g or less, and even more preferably 15 mg KOH / g or more and 30 mg KOH / g or less.

[0054] From the viewpoint of storage stability, the pH of the binder resin is preferably 4 to 11, preferably 4.5 to 11, preferably 5 to 10, and preferably 6 to 9.

[0055] The binder resin may be used alone or in combination of two or more types. The solid content of the binder resin in this embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, relative to the total amount of the colored adhesive composition. The solid content of the binder resin in this embodiment is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of the colored adhesive composition.

[0056] If the solid content of the binder resin is above the above preferred lower limit, the washability and abrasion resistance will be further improved. If the solid content of the binder resin is below the above preferred upper limit, the deinking properties will be further improved.

[0057] For example, the solid content of the binder resin is preferably 1% to 20% by mass, more preferably 3% to 15% by mass, and even more preferably 5% to 10% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0058] Crosslinking agent Examples of crosslinking agents include oxazolines, isocyanates, and carbodilites. One or more crosslinking agents may be used in combination. The crosslinking agent content (solid content) is preferably 0.1 to 1.5% by mass, and more preferably 0.2 to 1% by mass, relative to the total amount of the color paste composition of this embodiment, from the viewpoint of the texture of the fibers, the fastness of the printed material, and the deinking properties.

[0059] Organic solvents Examples of organic solvents include petroleum hydrocarbons and alcohols. Organic solvents may be used individually or in combination of two or more types. From the viewpoint of sharpness of the printed material, the content of the organic solvent is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 25.0% by mass, and even more preferably 10.0 to 20.0% by mass, relative to the total amount of the color paste composition of this embodiment.

[0060] Viscosity modifiers Examples of viscosity modifiers include diester stearate, cellulose, polyvinyl alcohol, and organic bentonite. Viscosity modifiers may be used individually or in combination of two or more types. From the viewpoint of the fastness of the printed material, the viscosity modifier content (solids) of the color paste composition of this embodiment is preferably 0.005 to 2.5% by mass, more preferably 0.010 to 1.5% by mass, and even more preferably 0.015 to 0.7% by mass.

[0061] Thickening agent Examples of thickening agents include polyacrylic acid, urethane-modified polyether, carboxymethylcellulose, and xanthan gum. One or more types of thickening agents may be used in combination. From the viewpoint of the fastness of the printed material, the content of the thickening agent (solids) is preferably 0.008 to 1.0% by mass, more preferably 0.015 to 0.5% by mass, and even more preferably 0.02 to 0.1% by mass, relative to the total amount of the color paste composition of this embodiment.

[0062] pH adjuster Examples of pH adjusters include ammonia, sodium hydroxide, potassium hydroxide, and organic amines. pH adjusters can be used as is, or they can be used as aqueous solutions, etc. pH adjusters may be used individually or in combination of two or more types. From the viewpoint of chemical resistance, the pH adjusting agent content is preferably 0.01 to 1.5% by mass, more preferably 0.03 to 1.0% by mass, and even more preferably 0.05 to 0.5% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0063] ≪Humectants≫ Examples of wetting agents include monoethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin. One or more types of humectants may be used in combination. From the viewpoint of the fastness of the printed material, particularly its washability and moisture-resistant friction fastness, the content of the wetting agent is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 1.0 to 2.5% by mass, relative to the total amount of the color paste composition of this embodiment.

[0064] ≪Moisturizer≫ Examples of moisturizers include urea, heparin, and petrolatum. Moisturizers may be used individually or in combination of two or more types. From the viewpoint of the fastness of the printed material, the content of the humectant is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 1.0 to 2.5% by mass, relative to the total amount of the color paste composition of this embodiment.

[0065] Flame retardant Examples of flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants, and antimony-based flame retardants. Flame retardants may be used in combination of one or more types. From the viewpoint of flame retardancy, the amount of flame retardant is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 20 to 30% by mass, based on the total amount of the colored adhesive composition of this embodiment.

[0066] ≪Water≫ Examples of water include deionized water, tap water, and distilled water. Water may be used alone or in combination of two or more types. From the viewpoint of printability, the water content is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 40% by mass, relative to the total amount of the color paste composition of this embodiment.

[0067] (Method for manufacturing printed fabric and deinked printed fabric) The printed fabric of this embodiment is characterized by being printed with the above-described color paste composition. Furthermore, the printed fabric of this embodiment can be manufactured by a method for manufacturing printed fabric, which includes a printing step in which the above-mentioned color paste composition is printed onto the fabric to obtain the printed fabric. Furthermore, the method for manufacturing a deinked printed cloth according to this embodiment includes a deinking step of mixing the printed cloth, a deinking agent, and a contact body, and applying an external force by bringing the contact body into contact with the printed cloth to obtain a deinked printed cloth.

[0068] [Printing process] The printing process involves printing the aforementioned color paste composition onto the fabric to obtain a printed fabric. Methods for printing the above-mentioned colored paste composition onto fabric include, for example, screen printing using a roller printer, flat screen printer, rotary screen printer, etc., with a squeegee made of rubber, urethane resin, etc. The screen used for screen printing is usually 60 to 300 mesh. After printing, a drying and heat treatment process is carried out at 100 to 150°C for 1 to 5 minutes to fix the colored paste composition to the fabric.

[0069] In addition to screen printing, various other printing methods such as gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating can also be used to print the above-mentioned colored paste composition onto fabric. Furthermore, the above-mentioned colored paste composition can also be applied to fabric by immersion (padding method), spray method, or inkjet method.

[0070] Examples of fabric materials include polyester, acrylic, polyethylene, polypropylene, nylon, cotton, vinylal, vinylon, ethylene vinyl alcohol fiber, polyvinyl chloride, vinylidene, modacryl, acrylate, aramid, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyarylate fiber, polylactic acid, polyurethane, fluorine fiber, polyimide, polyether ester elastomer, polyphenylene sulfide, alginate, elastodiene, elastoolefin, melamine fiber, polycarbonamide, trivinyl, polybenzimidazole, chitin fiber, carbon fiber, glass fiber, metal fiber, ceramic fiber, rayon, polynosic, modal, lyocell, cupro, acetate, triacetate, promix, protein fiber, and blends thereof. The weight per unit area of ​​polyester fabric, considering its use as a general advertising flag fabric, is estimated to be between 40.0 and 120.0 g / m². 2 Preferably, 50.0 to 100.0 g / m²2 This is more preferable, and 55.0 to 95.0 is even more preferable. The weight per unit area was calculated by measuring the weight of a 10cm square piece of fabric using a balance scale, and then using the obtained weight and the area of ​​the fabric.

[0071] [Deinking process] The deinking process involves applying external force to the printed fabric in the presence of a deinking agent to remove ink, thereby obtaining a deinked printed fabric.

[0072] The amount of deinking agent used is preferably 50 to 400 parts by mass, more preferably 75 to 300 parts by mass, per 1 part by mass of the printed fabric.

[0073] The processing temperature in the deinking process is preferably 45 to 100°C, more preferably 50 to 95°C, even more preferably 60 to 95°C, and particularly preferably 70 to 90°C.

[0074] The processing time in the deinking process is preferably 1 to 60 minutes, and more preferably 10 to 45 minutes.

[0075] The deinking process is preferably performed using rotational processing. Specifically, rotational processing at 10 to 1000 revolutions per minute is preferred, rotational processing at 10 to 600 revolutions per minute is more preferred, and rotational processing at 10 to 100 revolutions per minute is even more preferred.

[0076] The deinking process is preferably carried out using a stirrer. Examples of such agitators include rounder meters, stirrers, industrial washing machines, and decolorization / bleaching equipment. Among these, rounder meters and stirrers are preferred.

[0077] A rounder meter is a device in which a container containing stainless steel balls rotates, and these stainless steel balls agitate the liquid. A stirrer is a device that uses the force of magnets to rotate a magnetic rod called a rotor (or stirring bar) inside a container, thereby stirring a liquid.

[0078] When using a rounder meter in the deinking process, the diameter of the stainless steel ball is preferably 2 to 10 mm, more preferably 4 to 8 mm, and even more preferably 6 to 8 mm.

[0079] When using a rounder meter in the deinking process, the number of stainless steel balls is preferably 5 to 45, and more preferably 10 to 30.

[0080] When using a stirrer in the deinking process, the rotor is preferably tapered. Preferred tapered shapes are 10mm-Φ4, 20mm-Φ7, 25mm-Φ8, or 30mm-Φ8.

[0081] The deinking process is preferably a process in which the deinking agent, the contact body, and the printed fabric are mixed together, and an external force is applied by bringing the contact body into contact with the printed fabric. More specifically, it is preferable to use a rounder meter to mix the above-mentioned deinking agent, stainless steel balls, and the printed fabric in the container of the rounder meter, and to obtain a deinked printed fabric by applying external force by bringing the stainless steel balls into contact with the printed fabric.

[0082] Applications of printed fabrics include advertising banners and flags, clothing, sportswear, fashion items, bedding, household goods such as interior furnishings, car seats, and nonwoven fabrics.

[0083] <Deinking agent> Examples of deinking agents include those containing basic compounds and surfactants.

[0084] The pH of the deinking agent is preferably greater than 7 and 14 or less, more preferably between 8 and 14, even more preferably between 10 and 14, and particularly preferably between 11 and 14. If the pH of the deinking agent is within the above range, the deinking performance will be further improved.

[0085] In this specification, pH refers to the value obtained when measuring a deinking agent at 25°C using a pH meter (product name: pH meter F-71, manufactured by Horiba, Ltd.).

[0086] The deinking agent composition of this embodiment comprises a basic compound and a surfactant.

[0087] <Basic compounds> Basic compounds include basic inorganic compounds and basic organic compounds.

[0088] Basic inorganic compounds Examples of basic inorganic compounds include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal bicarbonates, and alkali metal carbonates. Examples of alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide. Examples of alkali metal bicarbonates include sodium bicarbonate and potassium bicarbonate. Examples of alkali metal carbonates include sodium carbonate and potassium carbonate.

[0089] Basic organic compounds Examples of basic organic compounds include amines. Examples of amines include ammonia, pyridine, arginine, lysine, triethylamine, and triethanolamine.

[0090] Among the basic compounds mentioned above, basic inorganic compounds are preferred, alkali metal hydroxides are preferred, and sodium hydroxide or potassium hydroxide is more preferred.

[0091] Basic compounds may be used individually or in combination of two or more. The content of the basic compound is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more, relative to the total amount of the deinking agent. The content of basic compounds is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.5% by mass or less, based on the total amount of deinking agent.

[0092] If the content of basic compounds is above the preferred lower limit mentioned above, the deinking properties will be further improved. If the content of basic compounds is below the preferred upper limit mentioned above, the impact on the printed fabric can be further reduced. Furthermore, the chemical risk of the deinking composition can be reduced, making it easier to implement recycling systems.

[0093] For example, the content of basic compounds is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 3.0% by mass or less, and even more preferably 0.5% by mass or more and 1.5% by mass or less, relative to the total amount of deinking agent.

[0094] <Surfactants> The surfactant may be any of the following: anionic surfactant, nonionic surfactant, cationic surfactant, or amphoteric surfactant.

[0095] The HLB value of the surfactant is preferably 1 to 18, more preferably 3 to 17, even more preferably 5 to 17, and particularly preferably 6 to 17.

[0096] When the HLB value of the surfactant is within the preferred range mentioned above, the deinking properties are further improved.

[0097] In this specification, "HLB (Hydrophile-Lipophile Balance)" is a value proposed by Griffin that indicates the balance between hydrophilic and lipophilic groups in a surfactant molecule. This HLB value can be experimentally determined by comparing the emulsifying power of various surfactants, but it can typically be determined from the following Equation 1. Equation 1: HLB value = 20 × weight % of hydrophilic portion of surfactant / molecular weight of surfactant

[0098] Among the surfactants mentioned above, nonionic surfactants are preferred.

[0099] Nonionic surfactants Preferred nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyethylene styrylated phenyl ethers, and polyoxyalkylated rivenzyl phenyl ethers. Preferred polyoxyalkylene alkyl ethers include polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene tridecyl ether, polyoxyethylene polyoxypropylene branched decyl ether, and polyoxyethylene lauryl ether. As the polyoxyalkylated tripenzylphenyl ether, polyoxyethylene tripenzylphenyl ether is preferred.

[0100] The HLB value of the polyoxyalkylene alkyl ether is preferably 1 to 15, more preferably 3 to 14.5, even more preferably 5 to 14, and particularly preferably 6 to 10.

[0101] The HLB value of polyoxyethylene styrylated phenyl ether is preferably 1 to 18, more preferably 10 to 17, even more preferably 12 to 17, and particularly preferably 13 to 16.

[0102] Among the nonionic surfactants listed above, polyoxyethylene styrylated phenyl ether is preferred.

[0103] Surfactants may be used individually or in combination of two or more types. The surfactant content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, relative to the total amount of the deinking agent. The surfactant content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less, relative to the total amount of the deinking agent.

[0104] If the surfactant content is above the preferred lower limit mentioned above, the deinking properties will be further improved. If the surfactant content is below the above-mentioned preferred upper limit, foaming will be less likely to occur, making it easier to rinse with water.

[0105] For example, the surfactant content is preferably 0.01% to 5.0% by mass, more preferably 0.05% to 3.0% by mass, and even more preferably 0.1% to 1.0% by mass, relative to the total amount of the deinking agent.

[0106] The deinking agent may contain optional components other than the basic compounds and surfactants mentioned above. Examples of such optional components include water, reducing agents, chelating agents, and flocculants.

[0107] ≪Water≫ Examples of water include deionized water, tap water, and distilled water. Water may be used alone or in combination of two or more types.

[0108] The water content is preferably 90 to 99.98% by mass, more preferably 93 to 99% by mass, and even more preferably 95 to 99% by mass, relative to the total amount of deinking agent.

[0109] Reducing agent Examples of reducing agents include hydrosulfite, thiourea dioxide, zinc sulfoxylate formaldehyde, and sodium sulfoxylate formaldehyde.

[0110] Chelating agents Examples of chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), gluconic acid, and hydroxyethylidenediphosphonic acid.

[0111] The method for manufacturing the deinked printed fabric of this embodiment may include optional steps other than the [deinking step] described above. Such optional steps include a washing step for washing the deinked printed fabric obtained in the [deinking step].

[0112] [Washing process] The washing process involves washing the deinked printed fabric obtained in the deinking process described above. Specifically, the washing process includes a water washing step in which the deinked printed fabric obtained in the deinking process described above is washed with water. The rinsing process may be carried out while applying external force, from the standpoint of cleaning effectiveness. Examples of external forces include those similar to those exemplified in the deinking process. The amount of water used depends on the applied external force, but is preferably 5,000 to 50,000 parts by mass, and more preferably 10,000 to 30,000 parts by mass, per 1 part by mass of the printed cloth. [Examples]

[0113] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0114] [Synthesis example of a deinking adhesive 1] First, a glycol raw material composed of ethylene glycol and diethylene glycol in a 1:1 molar ratio, and a dicarboxylic acid raw material composed of terephthalic acid and isophthalic acid in a 1:1 molar ratio were prepared. Next, 100 g of a polyol prepared by mixing the previously prepared dicarboxylic acid raw material with hydroxyl groups of the glycol raw material in a molar ratio (OH / COOH) of 1.19, 26.5 g of isophorone diisocyanate, 8.0 g of 2,2'-dimethylolpropionic acid, and 72.6 g of methyl ethyl ketone were charged into a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. The mixture was then reacted at 75°C for 8 hours under a nitrogen atmosphere to obtain a urethane resin intermediate. Next, 4.26 g of 25% by mass aqueous ammonia solution and 546 g of deionized water were added to the urethane resin intermediate, and the mixture was stirred at 55°C for 5 hours under a nitrogen atmosphere to obtain an emulsion. Then, by distilling off the solvent under reduced pressure in a 40°C atmosphere, the deinking and fixing agent 1, which is a urethane resin, was obtained as an aqueous dispersion (solid content 22.4% by mass).

[0115] [Example 2 of synthesis of deinking adhesive] In a stainless steel container, 200g of deionized water, 9g of DKS NL-180 polyoxyethylene lauryl ether, 8g of DKS NL-450F polyoxyethylene lauryl ether, and 2g of Hythenol LA-12 polyoxyethylene lauryl ether sulfate ammonium were thoroughly dissolved. Then, 60g of styrene monomer, 120g of ethyl acrylate, 180g of n-butyl acrylate, 50g of methacrylic acid, and 5g of n-dodecyl mercaptan were added and slowly emulsified to obtain an emulsion. Then, 300g of deionized water, 3g of DKS NL-180, and 20g of isopropyl alcohol were placed in a stainless steel separable flask, and 0.5g of ammonium persulfate, 0.8g of sodium disulfite, and 0.3g of 1% ferric chloride aqueous solution were added, and the mixture was heated to a 50°C atmosphere under nitrogen reflux. Then, by adding the above emulsion, 21.8 g of an aqueous solution of 1.8 g of ammonium persulfate, and 22.4 g of an aqueous solution of 2.4 g of sodium disulfite dropwise from each neck of the flask and allowing the mixture to react for about 3 hours, a deinking adhesive 2, which is an acrylic resin, was obtained as an aqueous dispersion (solid content 41.0% by mass).

[0116] [Synthesis example of deinking adhesive 3] Except for increasing the amount of methacrylic acid by 5 g and decreasing the amount of n-butyl acrylate by 5 g, deinkable adhesive 3, which is an acrylic resin, was obtained as an aqueous dispersion (solid content 41.1% by mass) in the same manner as in [Synthesis Example 2 of Deinkable Adhesive].

[0117] [Synthesis example of deinking adhesive 4] Except for reducing the amount of methacrylic acid by 5 g and increasing the amount of n-butyl acrylate by 5 g, a deinkable adhesive 4, which is an acrylic resin, was obtained as an aqueous dispersion (solid content 41.1% by mass) in the same manner as in [Synthesis Example 2 of Deinkable Adhesive].

[0118] [Synthesis example of deinking adhesive 5] Except for increasing the amount of n-dodecyl mercaptan by 2.5 g, a deinkable adhesive 5, which is an acrylic resin, was obtained as an aqueous dispersion (solid content 41.9% by mass) in the same manner as in [Synthesis Example 2 of Deinkable Adhesive].

[0119] [Synthesis example of deinking adhesive 6] Except for reducing the amount of n-dodecyl mercaptan by 2.5 g, a deinkable adhesive 6, which is an acrylic resin, was obtained as an aqueous dispersion (solid content 41.0% by mass) in the same manner as in [Synthesis Example 2 of Deinkable Adhesive].

[0120] [Synthesis example of deinking adhesive 7] Using the glycol and dicarboxylic acid raw materials described in [Synthesis Example 1 of Deinking Adhesive], 100 g of polyol with increased molecular weight was prepared by adjusting the molar ratio (OH / COOH) of hydroxyl groups of the glycol raw material to carboxylic acid groups of the dicarboxylic acid raw material to 1.13. This polyol was then charged with 16.0 g of isophorone diisocyanate, 3.5 g of 2,2'-dimethylolpropionic acid, and 65.4 g of methyl ethyl ketone. The mixture was reacted under a nitrogen atmosphere at 75°C for 8 hours to obtain a urethane resin intermediate. Next, 2.77 g of 25% by mass aqueous ammonia solution and 493 g of deionized water were added to the urethane resin intermediate, and the mixture was stirred under a nitrogen atmosphere at 55°C for 5 hours to obtain an emulsion. Then, by distilling off the solvent under reduced pressure in a 40°C atmosphere, the deinking and fixing agent 7, which is a urethane resin, was obtained as an aqueous dispersion (solid content 40.0% by mass).

[0121] [Synthesis example of deinking adhesive 8] 100 g of the polyol used in [Synthesis Example 7 of Deinking Adhesive] was charged with 20.8 g of isophorone diisocyanate, 8.1 g of 2,2'-dimethylolpropionic acid, and 69.7 g of methyl ethyl ketone in that order, and reacted under a nitrogen atmosphere at 75°C for 8 hours to obtain a urethane resin intermediate. Next, 4.29 g of 25% by mass aqueous ammonia solution and 523 g of deionized water were added to the urethane resin intermediate, and the mixture was stirred under a nitrogen atmosphere at 55°C for 5 hours to obtain an emulsion. Then, by distilling off the solvent under reduced pressure in a 40°C atmosphere, the deinking and fixing agent 8, which is a urethane resin, was obtained as an aqueous dispersion (solid content 23.2% by mass).

[0122] [Synthesis example of deinking adhesive 9] Using the glycol and dicarboxylic acid raw materials described in [Synthesis Example 1 of Deinking Adhesive], 100 g of polyol with increased molecular weight was prepared by adjusting the molar ratio (OH / COOH) of hydroxyl groups of the glycol raw material to carboxylic acid groups of the dicarboxylic acid raw material to 1.17. This polyol was then charged with 29.8 g of isophorone diisocyanate, 11.3 g of 2,2'-dimethylolpropionic acid, and 60.6 g of methyl ethyl ketone. The mixture was reacted under a nitrogen atmosphere at 75°C for 8 hours to obtain a urethane resin intermediate. Next, 6.0 g of 25% by mass aqueous ammonia solution and 572 g of deionized water were added to the urethane resin intermediate, and the mixture was stirred under a nitrogen atmosphere at 55°C for 5 hours to obtain an emulsion. Then, under reduced pressure and a 40°C atmosphere, the solvent was removed by distillation, and triethylamine was added to adjust the pH, thereby obtaining the deinking and fixing agent 9, which is a urethane resin, as an aqueous dispersion (solid content 24.9% by mass).

[0123] [Preparation of Binder Resin O-1] Binder resin O-1 (DEXCEL CLEAR CONC F-7, manufactured by DIC Corporation, solid content 30.5% by mass) was prepared.

[0124] [Preparation of Binder Resin O-2] Binder resin O-2 (DEXCEL CLEAR CONC L-202, manufactured by DIC Corporation, solid content 42.0% by mass) was prepared.

[0125] Table 1 shows the types of deinking adhesives and binder resins, their acid value, molecular weight, and pH, respectively. The measurement methods for each parameter are as follows.

[0126] [Measurement of acid value] The amount of acid in 1 g of resin (deinking adhesive or binder resin), calculated by titrating the acid with an alkali, was converted to the amount of potassium hydroxide in mg and measured according to JIS K 0070:1992. The results are shown in Table 1.

[0127] [Measurement of molecular weight] The weight-average molecular weight (Mw) of the urethane resin was measured under the following conditions. The results are shown in Table 1. Measurement device: High-speed GPC device (HLC-8220GPC manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. TSKgelG5000(7.8mml.D.×30cm)×1 piece TSKgel G4000 (7.8mm l.D. x 30cm) x 1 TSKgel G3000 (7.8mm l.D. x 30cm) x 1 TSKgel G2000 (7.8mm l.D. x 30cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40℃ Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard samples: Calibration curves were prepared using the following monodisperse polystyrene. (Monodisperse polystyrene) TSKgel Standard Polystyrene A-500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-1000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-2500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-5000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-1, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-2, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-4, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-10, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-20, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-40, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-80, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-128, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-288, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-550, manufactured by Tosoh Corporation.

[0128] The weight-average molecular weight (Mw) of the acrylic resin was measured under the following conditions. The results are shown in Table 1. Measurement device: High-speed GPC device (HLC-8420GPC manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. TSKgel-SuperAWN-H x 1 bottle Detector: RI (Differential Refractometer) Column temperature: 40℃ Eluent: 10mM LiBr DMF Flow rate: 0.6mL / min Injection volume: 30μL Standard samples: Calibration curves were prepared using the following monodisperse polystyrene. (Monodisperse polystyrene) TSKgel Standard Polystyrene A-500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-1000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-2500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-5000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-1, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-2, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-4, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-10, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-20, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-40, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-80, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-128, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-288, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-550, manufactured by Tosoh Corporation.

[0129] [Measuring pH] pH was measured at 25°C using a pH meter (Horiba, Ltd.: pH meter F-71). The results are shown in Table 1.

[0130] [Table 1]

[0131] [Preparation of adhesive for advertising flags] Deionized water, a humectant, and a wetting agent were added to the instant binder for textile printing, and then organic solvents were added in small amounts to emulsify the mixture. Furthermore, a pH adjuster was added and stirred, and finally a viscosity adjuster and a thickener were mixed in to prepare the base adhesive for advertising flags.

[0132] The details of each ingredient in the base adhesive for advertising flags are as follows: Instant binders for textile printing: Binder resin O-1 (DEXCEL CLEAR CONC F-7, manufactured by DIC Corporation) and binder resin O-2 (DEXCEL CLEAR CONC L-202, manufactured by DIC Corporation), both are acrylic resin emulsions. Moisturizer: Urea, manufactured by Mitsui Chemicals, Inc. Humectant: Monoethylene glycol, manufactured by Mitsubishi Chemical Corporation Organic solvent: Cactus Solvent P-20, petroleum hydrocarbon, manufactured by ENEOS Corporation. pH adjuster: 25% aqueous ammonia, manufactured by Wako Pure Chemical Industries, Ltd. Viscosity modifier: DEXCEL AGENT E, manufactured by DIC Corporation, solids content: 42% by mass Thickener: DEXCEL AGENT 15V, polyacrylic acid, manufactured by DIC Corporation, solids content: 88.0%

[0133] (Examples 1-16, Comparative Example 1) [Manufacturing of colored paste compositions] The colored adhesive compositions described in Tables 3 to 5 were produced by further mixing the prepared base adhesive for advertising flags with the following pigments 1 to 4, a deinking binder, and a crosslinking agent (DEXCEL AGENT GP CONC, oxazoline-based, manufactured by DIC Corporation, solids content: 28% by mass). Pigments 1-4 are all aqueous pigment dispersions manufactured by DIC Corporation. Pigment 1: DEXCEL BLACK HR CONC, Pigment content: 40.0% by mass Pigment 2: DEXCEL BLUE HR, Pigment content: 36.5% by mass Pigment 3: DEXCEL RED HBH, Pigment content: 35.5% by mass Pigment 4: DEXCEL LIGHT YELLOW HG, Pigment content: 33.5% by mass

[0134] [Preparation of test printable fabric] Polyester pongee (T. Pongee HR White, Weight: 57.0g / m) 2 A chloroprene rubber sheet (manufactured by Seihō Chemical Industry Co., Ltd.) was applied to a bracket (made of chloroprene rubber, hardness 60, thickness 5 mm), and then printed using a 135-mesh flat screen (2 cm x 4 cm rectangular pattern, 135 mesh, polyester screen, manufactured by Sanko Co., Ltd.) with a squeegee (made of chloroprene rubber, hardness 70, accessory for MH-5 type) using a test printing paste. Then, this was dried at 100°C for 1 minute using a dryer (MH-5 model, manufactured by Tsujii Dyeing Machinery Co., Ltd.), and then heat-treated at 150°C for 2 minutes using the same dryer (MH-5 model, manufactured by Tsujii Dyeing Machinery Co., Ltd.) to obtain a printed fabric. The obtained printed fabric was cut into a 3cm x 5cm rectangle so that a 2cm x 4cm rectangular pattern was in the center, thereby obtaining a test printed fabric with both white and printed areas. The printed side of the test specimen is considered the surface.

[0135] [Evaluation of deinking properties (front and back) and white area contamination] Five test printable cloths, 20 steel balls (diameter: 6 mm), and 100 mL of deinking agent (200 parts by mass per 1 part by mass of test printable cloth) were placed in the stainless steel container attached to the rounder meter (L-16Z-T, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). Then, using a rounder meter, the fabric was treated at 40 revolutions per minute for 15 minutes in an atmosphere of 85°C, and then 10,000 mL of tap water was sprayed in a shower-like manner over the five test print fabrics to wash both sides of them. The evaluation criteria for deinking properties are as follows, and the evaluation was performed on both the front and back surfaces of the test printed cloth. The evaluation criteria conformed to "JIS L 0804 2004, Grace Scale for Discoloration and Fading". The evaluation is on a 9-point scale, and a lower value indicates better deinking and superior deinking performance. The evaluation criteria for contamination of white areas are as follows: The evaluation criteria conformed to "JIS L 0805 2005, Grayscale for Contamination." The evaluation is on a 9-point scale, with higher values ​​indicating less white field contamination and thus less white field contamination. The results are shown in Tables 3-5.

[0136] [Table 2]

[0137] In Table 2, the sodium hydroxide is special grade sodium hydroxide manufactured by Kishida Chemical Co., Ltd., and the polyoxyethylene polyoxypropylene lauryl ether is DKS NL-DASH 404 (HLB=8) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0138] [Washfastness] Wash fastness conforms to "JIS L 0844:2011". Specifically, for wash fastness testing, five test print fabrics were placed in an accelerator (laboratory tester, LA-440, manufactured by Uenoyama Kiko Co., Ltd.), 100 mL of detergent solution (200 g of Marcel needle soap (manufactured by Daiichi Kogyo Seiyaku), 80 g of sodium bicarbonate (manufactured by Tosoh), and 3720 g of water) was added, and the fabrics were treated for 5 minutes at 1000 revolutions per minute in a sealed space with a bellows-like cylinder surface. After the washing process, the fabrics were removed and rinsed with 1000 mL of tap water, and then the wash fastness was checked after drying the test print fabrics at 50°C for 5 minutes using a heater. The evaluation criteria conformed to "JIS L 0804 2004, Grace Scale for Discoloration and Fading". The evaluation is on a 9-point scale, with higher values ​​indicating stronger printing and better wash fastness. The results are shown in Tables 3-5.

[0139] [Friction fastness (dry) and friction fastness (wet)] The friction fastness was tested in accordance with "JIS L 0849:2013". Specifically, the test involved attaching a test print fabric to a JSPS-type friction fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.: RT-200) using double-sided tape, attaching cotton calico to a jig, and rubbing it against 30 rectangular print surfaces with a force of 2N for 3 minutes and 20 seconds, performing 100 back-and-forth strokes. Then, I checked the degree of color transfer and the wear on the printed areas. For wet friction testing, cotton calico was moistened with water and tested with a 100% pickup rate. The following fabrics were used for the test printing. Polyester pongee (T. Pongee HR White, Weight: 57.0g / m) 2 A chloroprene rubber sheet (manufactured by Seihō Chemical Industry Co., Ltd.) was applied to a bracket (made of chloroprene rubber, hardness 60, thickness 5 mm), and then printed using a 135-mesh flat screen (2 cm x 4 cm rectangular pattern, 135 mesh, polyester screen, manufactured by Sanko Co., Ltd.) with a squeegee (made of chloroprene rubber, hardness 70, accessory for MH-5 type) using a test printing paste. Then, this was dried at 100°C for 1 minute using a dryer (MH-5 model, manufactured by Tsujii Dyeing Machinery Co., Ltd.), and then heat-treated at 150°C for 2 minutes using the same dryer (MH-5 model, manufactured by Tsujii Dyeing Machinery Co., Ltd.) to obtain a printed fabric. Then, a piece was cut out so that 5 x 6 rectangular patterns of 2 cm x 4 cm remained on each sheet, and this was used as a test printable fabric. The evaluation criteria conformed to "JIS L 0805 2005, Grayscale for Staining". There are nine evaluation levels, with higher values ​​indicating stronger printing and better abrasion fastness.

[0140] [Table 3]

[0141] [Table 4]

[0142] [Table 5]

[0143] As shown in Tables 3 to 5, the colored adhesive compositions of Examples 1 to 16 were found to have better washability and abrasion resistance, as well as good deinking properties, compared to the colored adhesive composition of Comparative Example 1, which does not contain a deinking agent.

[0144] While preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications are possible without departing from the spirit of the invention. The present invention is not limited by the foregoing description, but only by the scope of the appended claims.

Claims

1. It contains a pigment and a deinking adhesive, The weight-average molecular weight (Mw) of the deinking adhesive is 10,000 or more and 100,000 or less. The acid value of the deinking adhesive is 8 mg KOH / g or more and 45 mg KOH / g or less. A colored adhesive composition in which the deinking agent is a urethane resin or an acrylic resin.

2. The colored paste composition according to claim 1, wherein the content of the deinking agent is 1.0% by mass or more and 20.0% by mass or less, based on the total amount of the colored paste composition.

3. The colored adhesive composition according to claim 1 or 2, further comprising a binder resin having a weight-average molecular weight (Mw) greater than 100,000.

4. Furthermore, the colored paste composition according to claim 1 or 2 contains a crosslinking agent.

5. A printed fabric, which has been printed with the colored paste composition according to claim 1 or 2.

6. A method for producing a deinked printed fabric, comprising a deinking step of mixing the printed fabric described in claim 5, a deinking agent, and a contact body, and applying an external force by bringing the contact body into contact with the printed fabric to obtain a deinked printed fabric.

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