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

Abstract

A color paste composition comprising a pigment and a deinking fixing agent, wherein the deinking fixing agent contains a urethane resin (A1) having a glass transition temperature (Tg) of 50°C or lower.

Description

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

[0001] This invention relates to a colored paste composition, a printed fabric, and a method for producing a deinked printed fabric. This application claims priority under Japanese Patent Application No. 2025-018328, filed in Japan on February 6, 2025, the contents of which are incorporated herein by reference.

[0002] Advertising flags (nobori flags), which are rectangular pieces of cloth tied to a pole, are used as promotional tools and are displayed in front of various types of businesses, mainly restaurants. These advertising flags are printed using a colored paste composition. This colored paste composition is also used on clothing.

[0003] Patent Document 1 discloses a pigment printing agent containing a polymer (A) obtained by polymerizing polymerizable monomers including a polymerizable monomer having a carboxyl group (a1) and a polymerizable monomer having a hydrolyzable silyl group (a2), and titanium dioxide (B), characterized in that the film elongation of polymer (A) alone is in the range of 1,200 to 5,000%, and the 1,000% modulus is 0.1 MPa or higher. According to this pigment printing agent, even if titanium dioxide is contained as a pigment, the original texture of the fabric is not impaired when printed on the fabric, and the printed area has excellent wash resistance, abrasion resistance, etc., and the dyed over-color area has excellent wash resistance, so it is possible to obtain printed fabric with a natural texture and suppressed color fading during washing, etc.

[0004] International Publication No. 2016 / 190208

[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 color paste composition has excellent deinking properties. Furthermore, with the growing interest in sustainability in recent years, the environmental burden caused by the large-scale use of energy and water in the textile industry has become a concern. In particular, the enormous increase in greenhouse gas emissions due to the mass production and mass consumption of clothing is a social issue in recent years. Against this backdrop, there is a movement in the apparel industry to create a resource recycling system for products by recycling clothing. When printing patterns to add design elements to clothing, pigment printing agents can generally be used regardless of the type of fabric or fiber. Also, when printed materials are used as clothing, a pleasant feel against the skin is required, so a good texture is also desirable. On the other hand, from the perspective of recycling discarded clothing and textiles back into clothing and textiles, it is necessary to remove the pigments and fixing resins used to impart design. Therefore, it is preferable that these colored paste compositions have excellent deinking properties, and that the printed fabrics printed with these colored paste compositions have a good texture. However, colored paste compositions that generally use pigments as coloring agents require fixing resins to the fibers, resulting in printed fabrics with poor texture. Furthermore, conventional colored paste compositions, such as those described in Patent Document 1, primarily focus on maintaining fastness against friction during wear and washing, and prioritize adhesion to the fibers, so 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 texture and 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.

[0007] The inventors of the present invention have intensively studied a deinking fixing agent. As a result, it has been found that the above problems can be solved by using a urethane resin having a specific glass transition temperature (Tg) or lower as the deinking fixing agent, and the present invention has been achieved. Specifically, the present invention has adopted the following configurations. [1] A color paste composition containing a pigment and a deinking fixing agent, wherein the deinking fixing agent contains a urethane resin (A1) having a glass transition temperature (Tg) of 50°C or lower. [2] The color paste composition according to [1], wherein the content of the solid content of the deinking fixing agent is 0.1% by mass or more and 40% by mass or less based on the total amount of the color paste composition. [3] A printed cloth printed with the color paste composition according to [1] or [2]. [4] A method for producing a deinked printed cloth, comprising a deinking step of mixing the printed cloth according to [3], 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.

[0008] According to the present invention, it is possible to provide a color paste composition having good texture and good deinking property, a printed cloth printed with the color paste composition, and a method for producing a deinked printed cloth obtained by deinking the printed cloth.

[0009] (Color paste composition) The color paste composition of the present embodiment contains a pigment and a deinking fixing agent.

[0010] <Pigment> A pigment is a powder used for coloring that is insoluble in water or oil. The pigment may be a pigment dispersion. The pigment content in the pigment dispersion is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, and still more preferably 30 to 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 oxide, zinc white, lead white, 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 molybdate orange; ferrocyanide pigments such as ultramarine blue; sulfide pigments such as cadmium yellow, cadmium red, zinc sulfide, and barium sulfide; ultramarine blue, calcium carbonate, cobalt violet, yellow iron oxide, carbon black, etc.

[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; condensed polycyclic pigments such as anthraquinone yellow, dianthraquinonyl red, indanthrene blue, thioindigo Bordeaux, 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] The pigment and pigment dispersion may be used individually or in combination of two or more. 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, relative to 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, relative to 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 pigment dispersion content is above the preferred lower limit mentioned above, washability and abrasion resistance will be further improved. If the pigment dispersion content is below the preferred upper limit mentioned above, deinking properties will be further improved.

[0016] For example, the pigment dispersion content is preferably 1% to 20% by mass, more preferably 5% to 15% by mass, and even more preferably 8% to 12% by mass, relative to the total amount of the colored adhesive composition of this embodiment. Furthermore, the pigment dispersion content may be 1% to 7% by mass, or 1% to 5% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0017] The pigment content is preferably 0.002% by mass or more, more preferably 0.02% by mass or more, even 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 colored paste composition of this embodiment. The pigment content is preferably 12% by mass or less, more preferably 9% by mass or less, even more preferably 7.2% by mass or less, and particularly preferably 6% by mass or less, based on the total amount of the colored paste composition of this embodiment. Furthermore, the pigment content may be 4.2% by mass or less, or even 3% by mass or less, based on the total amount of the colored paste composition of this embodiment.

[0018] If the pigment content is above the preferred lower limit mentioned above, washability and abrasion resistance will be further improved. If the pigment content is below the preferred upper limit mentioned above, deinking properties will be further improved.

[0019] For example, the pigment content is preferably 0.2% to 12% by mass, more preferably 1% to 9% by mass, and even more preferably 1.6% to 7.2% by mass, relative to the total amount of the colored adhesive composition of this embodiment. Furthermore, the pigment content may be 0.2% to 4.2% by mass, or 0.2% to 3% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0020] <Deinking Fixative> The deinking fixative is an ingredient that enhances the fixation of the pigment in the color paste composition to the printed fabric, and is an ingredient that is easily washed away during the deinking process. The deinking fixative is preferably an aqueous dispersion of resin. The solid content of the deinking fixative is preferably 10 to 55% by mass, preferably 15 to 50% by mass, preferably 20 to 45% by mass, preferably 20 to 40% by mass, and preferably 20 to 35% by mass.

[0021] 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 lower, more preferably 40 mg KOH / g or lower, and even more preferably 30 mg KOH / g or lower.

[0022] 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 preferred upper limit mentioned above, the deinking ability will be further improved.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] In this specification, pH refers to the value measured at 25°C using a pH meter (Horiba, Ltd.: pH meter F-71).

[0027] The deinking adhesive contains a urethane resin (A1) with a glass transition temperature (Tg) of 50°C or lower.

[0028] ≪Urethane Resin (A1)≫ The glass transition temperature (Tg) of urethane resin (A1) is 50°C or lower, preferably 40°C or lower, and more preferably 30°C or lower. The glass transition temperature (Tg) of urethane resin (A1) is preferably 1°C or higher, more preferably 3°C or higher, and even more preferably 4°C or higher.

[0029] A glass transition temperature (Tg) of urethane resin (A1) of 50°C or lower results in a good texture. A glass transition temperature (Tg) of urethane resin (A1) of 50°C or lower results in an even better texture. A glass transition temperature (Tg) of urethane resin (A1) of 50°C or lower results in an even better texture. A glass transition temperature (Tg) of urethane resin (A1) of 50°C or lower results in an even better texture. Washability and abrasion resistance are improved when the glass transition temperature (Tg) of urethane resin (A1) is above the preferred lower limit.

[0030] For example, the glass transition temperature (Tg) of the urethane resin (A1) is preferably 1°C or more and 50°C or less, more preferably 3°C or more and 40°C or less, and even more preferably 4°C or more and 30°C or less.

[0031] The glass transition temperature (Tg) of the urethane resin (A1) can be measured using a differential scanning calorimetry analyzer (device name "DSC Q-100", manufactured by TA Instruments). If the colored adhesive composition of this embodiment contains multiple urethane resins, it is sufficient that the glass transition temperature (Tg) of at least one of the urethane resins is 50°C or lower. That is, when the glass transition temperature (Tg) of the urethane resin is measured using a differential scanning calorimetry analyzer, it is sufficient that at least one baseline shift (step-like change) due to glass transition is observed at 50°C or lower in the DSC thermogram.

[0032] The glass transition temperature (Tg) of urethane resin can be measured specifically as follows: <Film Preparation> First, the urethane resin is diluted with deionized water to a non-volatile content of 10%, cast into a mold, and dried for 24 hours at 23°C and 65% RH to create a film with a thickness of 150 μm. <Tg Measurement> Next, 5 mg of the cut film is weighed into an aluminum open pan. Then, using a differential scanning calorimetry analyzer (device name "DSC Q-100", manufactured by TA Instruments Co., Ltd.), the measurement is repeated twice under the conditions of a temperature range of -70 to 150°C, a heating rate of 10°C / min, and rapid cooling, and the glass transition temperature obtained in the second measurement is adopted as the measured value.

[0033] Furthermore, the glass transition temperature (Tg) of the urethane resin in the colored paste composition and the printed material can be measured as follows. The glass transition temperature (Tg) of the urethane resin in the colored paste composition can be measured by the method described above. This is because the other components (e.g., pigments) contained in the colored paste composition are present in small amounts and have little effect on the measurement of the glass transition temperature (Tg). The glass transition temperature (Tg) of the urethane resin in the printed material can be measured by the method described above after extracting the urethane resin from the colored paste composition fixed to the printed material with a solvent.

[0034] The weight-average molecular weight (Mw) of the urethane resin (A1) is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 65,000 or less. The weight-average molecular weight (Mw) of the urethane resin (A1) is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more.

[0035] If the weight-average molecular weight (Mw) of the urethane resin (A1) is 100,000 or less, the deinking properties of the colored adhesive composition of this embodiment are improved. Furthermore, if the weight-average molecular weight (Mw) of the urethane resin (A1) is below the above preferred upper limit, the deinking properties are further improved. If the weight-average molecular weight (Mw) of the urethane resin (A1) is above the above preferred lower limit, the washability and abrasion resistance are further improved.

[0036] For example, the weight-average molecular weight (Mw) of the urethane resin (A1) is preferably 10,000 or more and 100,000 or less, more preferably 20,000 or more and 80,000 or less, and even more preferably 30,000 or more and 65,000 or less.

[0037] The weight-average molecular weight (Mw) of urethane resin (A1) refers to the value measured under the following conditions. Measurement device: High-speed GPC instrument (HLC-8220GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 ml. D. × 30 cm) × 1 TSKgel G4000 (7.8 ml. D. × 30 cm) × 1 TSKgel G3000 (7.8 ml. D. × 30 cm) × 1 TSKgel G2000 (7.8 ml. D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene. (Monodisperse polystyrene) TSKgel manufactured by Tosoh Corporation 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] The urethane resin (A1) contains constituent units derived from polyol compounds, dicarboxylic acid compounds, isocyanate compounds, hydroxycarboxylic acid compounds, etc. Examples of constituent units derived from polyol compounds include those derived from ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, and 1,4-butanediol. Specific examples of constituent units derived from dicarboxylic acid compounds include those derived from terephthalic acid, isophthalic acid, adipic acid, sebaciic acid, and phthalic anhydride. Specific examples of constituent units derived from isocyanate compounds include those derived from tolylene diisocyanate and 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.

[0039] The glass transition temperature (Tg) of urethane resins can be controlled by selecting monomers. For example, the glass transition temperature (Tg) of urethane resins can be lowered by using polyol compounds with relatively long carbon chains. The glass transition temperature (Tg) of urethane resins can be lowered by combining linear polyols or branched polyols having preferably 3 or more carbon atoms, preferably 3 to 6 carbon atoms, as constituent units of the polyol, and aliphatic dicarboxylic acids having preferably 3 or more carbon atoms, preferably 3 to 8 carbon atoms, as constituent units of the dicarboxylic acid.

[0040] The urethane resin (A1) may be used alone or in combination of two or more types. The solid content of the urethane resin (A1) is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 3.0% by mass or more, relative to the total amount of the colored adhesive composition of this embodiment. It is also preferably 10.0% by mass or more, and even more preferably 15.0% by mass or more. The solid content of the urethane resin (A1) is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment. It is also preferably 25% by mass or less, and even more preferably 20% by mass or less.

[0041] If the content of urethane resin (A1) is above the preferred lower limit above, the washability and abrasion resistance will be further improved. If the content of urethane resin (A1) is below the preferred upper limit above, the deinking properties will be further improved.

[0042] For example, the solid content of urethane resin (A1) is preferably 0.1% to 40% by mass, more preferably 1.0% to 35% by mass, and even more preferably 3.0% to 30% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0043] The content of urethane resin (A1) in the total amount of the deinking adhesive is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. The colored adhesive composition of this embodiment may contain only urethane resin (A1) as the deinking adhesive.

[0044] The deinking adhesive may contain other deinking adhesives (A2) besides the urethane resin (A1) described above.

[0045] <<Other deinking adhesives (A2)>> Other deinking adhesives (A2) specifically include acrylic resins with a weight-average molecular weight (Mw) of 100,000 or less, and urethane resins with a glass transition temperature (Tg) of over 50°C.

[0046] [Acrylic resin with a weight-average molecular weight (Mw) of 100,000 or less] 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, the styrene-acrylic resin preferably has constituent units derived from methacrylic acid.

[0047] Examples of acrylic acid esters include ethyl acrylate and n-butyl acrylate. Examples of acrylamides include N-methylolacrylamide.

[0048] 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.

[0049] 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 preferred upper limit, the deinking properties are further improved. When the weight-average molecular weight (Mw) of the acrylic resin is above the above preferred lower limit, the washability and abrasion resistance are further improved.

[0050] 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.

[0051] The weight-average molecular weight (Mw) of the 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 unmeasurable, and it is assumed that the weight-average molecular weight (Mw) is greater than 100,000. Measurement device: High-speed GPC device (HLC-8420GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel-SuperAWN-H x 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: 10 mM LiBr DMF Flow rate: 0.6 mL / min Injection volume: 30 μL (10 mM LiBr DMF solution with a sample concentration of 0.4 mass%) Standard samples: Calibration curves were prepared using the following monodisperse polystyrenes. (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)

[0052] Acrylic resins with a weight-average molecular weight (Mw) of 100,000 or less may be used individually or in combination of two or more types. The solid content of acrylic resins with a weight-average molecular weight (Mw) of 100,000 or less is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, relative to the total amount of the colored adhesive composition of this embodiment. The solid content of acrylic resins with a weight-average molecular weight (Mw) of 100,000 or less is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment.

[0053] If the content of acrylic resin with a weight-average molecular weight (Mw) of 100,000 or less is above the preferred lower limit mentioned above, washability and abrasion resistance will be further improved. If the content of acrylic resin with a weight-average molecular weight (Mw) of 100,000 or less is below the preferred upper limit mentioned above, deinking properties will be further improved.

[0054] For example, the content of acrylic resin as solids with a weight-average molecular weight (Mw) of 100,000 or less is preferably 0.3% by mass or more and 5.0% by mass or less, more preferably 0.5% by mass or more and 4.0% by mass or less, and even more preferably 1.0% by mass or more and 3.0% by mass or less, relative to the total amount of the color adhesive composition of this embodiment.

[0055] [Urethane resin with glass transition temperature (Tg) above 50°C] The glass transition temperature (Tg) of the urethane resin is above 50°C, preferably 51°C or higher. The glass transition temperature (Tg) of the urethane resin is preferably 75°C or lower, and more preferably 60°C or lower.

[0056] When the glass transition temperature (Tg) of the urethane resin is within the above preferred range, the texture becomes even better.

[0057] For example, the glass transition temperature (Tg) of the urethane resin is preferably greater than 50°C and 75°C or less, and more preferably 51°C or more and 60°C or less.

[0058] Urethane resins with a glass transition temperature (Tg) exceeding 50°C contain constituent units derived from polyol compounds, isocyanate compounds, hydroxycarboxylic acid compounds, and the like.

[0059] Examples of constituent units derived from polyol compounds include those derived from terephthalic acid, isophthalic acid, ethylene glycol, diethylene glycol, polypropylene glycol, and polycarbonate diols (such as those derived from 1,6-hexanediol).

[0060] Specific examples of constituent units derived from isocyanate compounds include those derived from isophorone diisocyanate, tolylene diisocyanate, and 4,4'-methylenebis(cyclohexyl isocyanate).

[0061] Specific examples of constituent units derived from hydroxycarboxylic acid compounds include those derived from 2,2'-dimethylolpropionic acid and those derived from 2,2'-dimethylolbutanoic acid.

[0062] Examples of constituent units derived from amine compounds include those derived from triethylamine, piperazine, and hydrazine.

[0063] The weight-average molecular weight (Mw) of the urethane resin is preferably greater than 100,000, more preferably 105,000 or more, and even more preferably 110,000 or more. The weight-average molecular weight (Mw) of the urethane resin is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 250,000 or less.

[0064] If the weight-average molecular weight (Mw) of the urethane resin is above the preferred lower limit mentioned above, the washability and abrasion resistance are further improved. If the weight-average molecular weight (Mw) of the urethane resin is below the preferred upper limit mentioned above, the deinking properties are further improved.

[0065] The weight-average molecular weight (Mw) of urethane resin refers to the value measured under the following conditions. Measurement device: High-speed GPC instrument (HLC-8220GPC manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 ml. D. × 30 cm) × 1 TSKgel G4000 (7.8 ml. D. × 30 cm) × 1 TSKgel G3000 (7.8 ml. D. × 30 cm) × 1 TSKgel G2000 (7.8 ml. D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene. (Monodisperse polystyrene) TSKgel manufactured by Tosoh Corporation 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)

[0066] A urethane resin having a glass transition temperature (Tg) above 50°C may be used alone or in combination of two or more types. The solid content of the urethane resin having a glass transition temperature (Tg) above 50°C is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and even more preferably 3.0% by mass or more, relative to the total amount of the colored adhesive composition of this embodiment. The solid content of the urethane resin having a glass transition temperature (Tg) above 50°C is preferably 10% by mass or less, more preferably 8.5% by mass or less, and even more preferably 7.0% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment.

[0067] If the content of urethane resin with a glass transition temperature (Tg) above 50°C is above the preferred lower limit mentioned above, washability and abrasion resistance will be further improved. If the content of urethane resin with a glass transition temperature (Tg) above 50°C is below the preferred upper limit mentioned above, deinking properties will be further improved.

[0068] For example, the content of urethane resin with a glass transition temperature (Tg) above 50°C as solid content is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1.0% by mass or more and 8.5% by mass or less, and even more preferably 3.0% by mass or more and 7.0% by mass or less, relative to the total amount of the colored adhesive composition of this embodiment.

[0069] <Optional Components> The colored adhesive composition of this embodiment may contain optional components. Examples of optional components include binder resin, crosslinking agent, organic solvent, viscosity modifier, thickener, pH adjuster, wetting agent, humectant, flame retardant, and water.

[0070] <Binder Resin> The colored adhesive composition of this embodiment preferably contains a binder resin. The binder resin is a resin with a weight-average molecular weight (Mw) of more than 100,000. However, the urethane resin mentioned above is not included in the binder resin. 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.

[0071] The acid value of the binder resin is preferably 8 mg KOH / g or higher, more preferably 15 mg KOH / g or higher. The acid value of the binder resin is preferably 45 mg KOH / g or lower, more preferably 40 mg KOH / g or lower, and even more preferably 30 mg KOH / g or lower.

[0072] 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 preferred upper limit mentioned above, the deinking properties will be further improved.

[0073] 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.

[0074] 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.

[0075] The binder resin may be used alone or in combination of two or more types. The solid content of the binder resin 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 of this embodiment. The solid content of the binder resin 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 of this embodiment. Furthermore, the solid content of the binder resin may be 5% by mass or less, or the binder resin may not be included at all.

[0076] If the solid content of the binder resin is above the preferred lower limit mentioned above, the washability and abrasion resistance will be further improved. If the solid content of the binder resin is below the preferred upper limit mentioned above, the deinking properties will be further improved.

[0077] For example, the content as the solid content of the binder resin is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and still more preferably 5% by mass or more and 10% by mass or less with respect to the total amount of the color paste composition of the present embodiment.

[0078] <<Crosslinking agent>> Examples of the crosslinking agent include oxazoline - based, isocyanate - based, carbodiimide - based, silane coupling agents, etc. The crosslinking agent may be used alone or in combination of two or more. The content (solid content) of the crosslinking agent is preferably 0.1 to 1.5% by mass, more preferably 0.2 to 1% by mass with respect to the total amount of the color paste composition of the present embodiment from the viewpoints of the texture of the fiber, the fastness of the printed matter, and the deinking property.

[0079] - Silane coupling agent As the silane coupling agent, a compound represented by the following general formula (i) is preferable.

[0080] [In general formula (i), R ｉ１ , R ｉ２ , and R ｉ３ each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, at least one represents an alkoxy group having 1 to 10 carbon atoms, L ｉ１ represents a single bond or a spacer group, and X ｉ１ represents an organic functional group. ]

[0081] The alkyl group having 1 to 10 carbon atoms in R < ｉ１ , R ｉ２ [[ID=XX]], and R ｉ３ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and is preferably a linear alkyl group having 1 to 10 carbon atoms. [[ID=3XX]]

[0082] The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3.

[0083] The alkyl groups having 1 to 10 carbon atoms in R ｉ１ , R ｉ２ , and R ｉ３The alkoxy group having 1 to 10 carbon atoms in this product is a linear, branched, or cyclic alkoxy group having 1 to 10 carbon atoms, and is preferably a linear alkoxy group having 1 to 10 carbon atoms.

[0084] The number of carbon atoms in the alkoxy group is preferably 1 to 6, and more preferably 1 to 3.

[0085] R ｉ１ , R ｉ２ , R ｉ３ A concrete example is the formula (R ｉ１／２／３ -1) to (R ｉ１／２／３ Examples of bases represented by -11) include the following.

[0086] [Formula (R ｉ１／２／３ -1) to (R ｉ１／２／３ -11) In this diagram, the black dots represent bonds to silicon atoms (Si).

[0087] R ｉ１ , R ｉ２ , and R ｉ３ Among the alkyl groups having 1 to 10 carbon atoms, linear alkyl groups having 1 to 6 carbon atoms are preferred from the viewpoint of steric hindrance around the Si atom, and methyl groups are more preferred.

[0088] R ｉ１ , R ｉ２ , and R ｉ３ Among the above, the alkoxy group having 1 to 10 carbon atoms is preferably a linear alkoxy group having 1 to 6 carbon atoms from the viewpoint of hydrolysis, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.

[0089] R ｉ１ , R ｉ２ , and R ｉ３ Of the above, it is preferable that two or more are alkoxy groups having 1 to 10 carbon atoms, and more preferably that all are alkoxy groups having 1 to 10 carbon atoms.

[0090] L ｉ１This represents a single bond or a spacer group. A spacer group is a flexible group. More specifically, a spacer group represents an alkylene group having 1 to 15 carbon atoms. One or more -CH groups are present in the alkylene group. ２ Each of the - atoms may be independently substituted with -O-. However, when the alkylene group is substituted with -O-, oxygen atoms do not directly bond to each other. The alkylene group is a linear, branched, or cyclic alkylene group, and a linear alkylene group is preferred. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 6. L ｉ１ A specific example of an alkylene group represented by formula (L ｉ１ -1) to (L ｉ１ Examples include the base represented in -4).

[0091] [Formula (L ｉ１ -1) to (L ｉ１ -4) In this diagram, the black dots represent bonds to silicon atoms (Si), and the white dots represent X ｉ１ [Represents a binding operation to .]

[0092] L ｉ１ From the viewpoint of affinity with resins and solvents, the above formula (L ｉ１ -2) ~ (L ｉ１ A group represented by any of the above formulas (L) is preferred, or a single bond. ｉ１ -2) The base represented by the above formula (L ｉ１ -3) A group represented by the above formula (L ｉ１ It is even more preferable that the group is represented by -3).

[0093] X ｉ１ This represents an organic functional group. An organic functional group is a functional group that is highly reactive with the binder resin.

[0094] Examples of organic functional groups include groups containing epoxy groups, amino groups, mercapto groups, vinyl groups, isocyanate groups, amine groups, acrylic groups, methacrylic groups, urea groups, and imine groups.

[0095] X ｉ１ A concrete example is the equation (X ｉ１ -1) to (X ｉ１ Examples include the groups represented in -13).

[0096] [Formula (X ｉ１ -1) to (X ｉ１ -13) Among them, the black spot is L ｉ１ [Represents a binding operation to .]

[0097] X ｉ１ From the perspective of compatibility with the binder resin, the above formula (X ｉ１ -1) The base represented by the above formula (X ｉ１ -3) ~ (X ｉ１ -5) The base represented by the above formula (X ｉ１ A base represented by -10), or the above formula (X ｉ１ It is preferable that the group is represented by the above formula (X ｉ１ -1) The base represented by the above formula (X ｉ１ -3) The base represented by the above formula (X ｉ１ A base represented by -5), or the above formula (X ｉ１ It is more preferable that the group is represented by the above formula (X ｉ１ It is even more preferable that the group is represented by -1).

[0098] Examples of compounds represented by general formula (i) include those represented by the following chemical formulas (i-1) to (i-24).

[0099]

[0100] Among the compounds represented by general formula (i), the compounds represented by chemical formula (i-1), chemical formula (i-2), chemical formula (i-5), chemical formula (i-10), chemical formula (i-11), chemical formula (i-15), chemical formula (i-21), and chemical formula (i-23) are preferred, the compounds represented by chemical formula (i-1), chemical formula (i-2), chemical formula (i-15), chemical formula (i-21), and chemical formula (i-23) are more preferred, and the compounds represented by chemical formula (i-1) and chemical formula (i-2) are even more preferred.

[0101] One or more silane coupling agents may be used in combination. From the viewpoint of achieving both fastness and deinking properties, the content of the silane coupling agent is preferably 0.1 to 5.0% by mass, more preferably 0.3 to 2.5% by mass, even more preferably 1.0 to 2.5% by mass, and particularly preferably 1.5 to 2.5% by mass, relative to the total amount of the colored adhesive composition of this embodiment.

[0102] Furthermore, when using two types of silane coupling agents in combination, the mass ratio of the first silane coupling agent to the second silane coupling agent is preferably 99:1 to 1:99, and preferably 60:40 to 40:60, from the viewpoint of achieving both robustness and deinking properties.

[0103] <<Organic Solvents>> Examples of organic solvents include petroleum hydrocarbons and alcohols. One or more organic solvents may be used in combination. 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.

[0104] <Viscosity Modifiers> Examples of viscosity modifiers include stearate diester, cellulose, polyvinyl alcohol, and organic bentonite. One or more viscosity modifiers may be used in combination. From the viewpoint of the fastness of the printed material, the content (solids) of the viscosity modifier 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, relative to the total amount of the color paste composition of this embodiment.

[0105] <<Thickening Agents>> Examples of thickening agents include polyacrylic acid, urethane-modified polyether, carboxymethylcellulose, and xanthan gum. One or more thickening agents may be used in combination. From the viewpoint of the fastness of the printed material, the content (solids) of the thickening agent 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.

[0106] <pH Adjusting Agents> Examples of pH adjusting agents include ammonia, sodium hydroxide, potassium hydroxide, and organic amines. pH adjusting agents may be used as is or as aqueous solutions. One or more pH adjusting agents may be used in combination. From the viewpoint of chemical resistance, the content of the pH adjusting agent 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.

[0107] <Wetting Agents> Examples of wetting agents include monoethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin. One or more wetting agents may be used in combination. From the viewpoint of the fastness of the printed material, particularly its washability and moisture-resistant friction fastness, the wetting agent content 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.

[0108] <Moisturizers> Examples of moisturizers include urea, heparin, and petrolatum. One or more moisturizers may be used in combination. From the viewpoint of the fastness of the printed material, the content of the moisturizer 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.

[0109] <<Flame Retardants>> Examples of flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants, and antimony-based flame retardants. One or more types of flame retardants may be used in combination. From the viewpoint of flame retardancy, the content of the 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.

[0110] <Water> Examples of water include deionized water, tap water, and distilled water. One type of water may be used alone, or two or more types may be used in combination. 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.

[0111] (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. The printed fabric of this embodiment can be manufactured by a method for manufacturing printed fabric that includes a printing step of obtaining printed fabric by printing the above-described color paste composition onto a cloth. Furthermore, the method for manufacturing deinked printed fabric of this embodiment includes a deinking step of mixing the printed fabric, 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 deinked printed fabric.

[0112] [Printing Process] The printing process is a process of obtaining printed fabric by printing the above-mentioned color paste composition onto the fabric. Methods for printing the above-mentioned color paste composition onto the 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 performed at 100 to 150°C for 1 to 5 minutes to fix the color paste composition to the fabric.

[0113] In addition to the screen printing method described above, 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.

[0114] 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, when used as a general advertising flag fabric, is 40.0 to 120.0 g / m². ２ Preferably, 50.0 to 100.0 g / m ２More preferably, 55.0 to 95.0 is even more preferable. The weight per unit area of ​​cotton fabric should be 100 to 140 g / m from the viewpoint of texture. ２ Preferably, 105 to 135 g / m ２ More preferably, 110 to 130 is even more preferable. Examples of polyester-cotton blended fibers include T / C broadcloth. From the viewpoint of texture, the weight per unit area of ​​T / C fabric should be 95 to 135 g / m². ２ Preferably, 100 to 130 g / m ２ A value of 105 to 125 is more preferable. The weight per unit area was calculated by measuring the weight of a piece of fabric cut into 10 cm squares using a balance scale, and using the obtained weight and the area of ​​the fabric.

[0115] [Deinking Process] The deinking process is a process in which ink is removed from the printed fabric by applying external force in the presence of a deinking agent, thereby obtaining a deinked printed fabric.

[0116] 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 cloth.

[0117] 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.

[0118] The processing time in the deinking process is preferably 1 to 60 minutes, and more preferably 10 to 45 minutes.

[0119] The deinking process is preferably performed using a rotational process. Specifically, it is preferable to perform a rotational process at 10 to 1000 revolutions per minute, more preferably at 10 to 600 revolutions per minute, and even more preferably at 10 to 100 revolutions per minute.

[0120] The deinking process is preferably carried out using a stirrer. Examples of such stirrers include rounder meters, stirrers, industrial washing machines, and decolorization / bleaching equipment. Among these, rounder meters and stirrers are preferred.

[0121] 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 in which a magnetic rod called a rotor (agitator) rotates inside a container using the force of a magnet to agitate the liquid.

[0122] 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.

[0123] 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.

[0124] When using a stirrer in the deinking process, the rotor is preferably tapered. Preferred tapered shapes are 10 mm - Φ4, 20 mm - Φ7, 25 mm - Φ8, or 30 mm - Φ8.

[0125] The deinking process is preferably a process in which the above-mentioned deinking agent, 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, mix the above-mentioned deinking agent, stainless steel ball, and the printed fabric in the container of the rounder meter, and obtain a deinked printed fabric while applying an external force by bringing the stainless steel ball into contact with the printed fabric.

[0126] 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.

[0127] <Deinking agents> Examples of deinking agents include those containing basic compounds and surfactants.

[0128] 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.

[0129] 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.).

[0130] The deinking agent composition of this embodiment comprises a basic compound and a surfactant.

[0131] <Basic Compounds> Examples of basic compounds include basic inorganic compounds and basic organic compounds.

[0132] 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.

[0133] Basic Organic Compounds: Examples of basic organic compounds include amines. Specifically, examples of amines include ammonia, pyridine, arginine, lysine, triethylamine, and triethanolamine.

[0134] 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.

[0135] The basic compound may be used alone 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, based on the total amount of the deinking agent. The content of the basic compound 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 the deinking agent.

[0136] If the content of basic compounds is above the preferred lower limit mentioned above, the deinking performance 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. In addition, the chemical risk of the deinking composition can be reduced, making it easier to implement recycling systems.

[0137] 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.

[0138] <Surfactants> The surfactant may be any of the following: anionic surfactant, nonionic surfactant, cationic surfactant, or amphoteric surfactant.

[0139] 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.

[0140] The deinking properties are further improved when the HLB value of the surfactant is within the preferred range described above.

[0141] 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. While the HLB value can be experimentally determined by comparing the emulsifying power of various surfactants, it can typically be calculated using the following formula 1: Formula 1: HLB value = 20 × weight % of hydrophilic portion of surfactant / molecular weight of surfactant

[0142] Among the surfactants mentioned above, nonionic surfactants are preferred.

[0143] <Nonionic Surfactants> As nonionic surfactants, polyoxyalkylene alkyl ethers, polyoxyethylene styrylated phenyl ethers, and polyoxyalkylated tripenzylphenyl ethers are preferred. As polyoxyalkylene alkyl ethers, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene tridecyl ether, polyoxyethylene polyoxypropylene branched decyl ether, polyoxyethylene lauryl ether, etc. are preferred. As polyoxyalkylated tripenzylphenyl ethers, polyoxyethylene tripenzylphenyl ether, etc. are preferred.

[0144] 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.

[0145] 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.

[0146] Among the nonionic surfactants listed above, polyoxyethylene styrylated phenyl ether is preferred.

[0147] The surfactant may be used alone 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, based on 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, based on the total amount of the deinking agent.

[0148] 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 preferred upper limit mentioned above, foaming will be less likely to occur, making it easier to rinse with water.

[0149] For example, the surfactant content is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.05% by mass or more and 3.0% by mass or less, and even more preferably 0.1% by mass or more and 1.0% by mass or less, relative to the total amount of the deinking agent.

[0150] 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.

[0151] ≪Water≫ Examples of water include deionized water, tap water, and distilled water. One type of water may be used alone, or two or more types may be used in combination.

[0152] 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.

[0153] <<Reducing Agents>> Examples of reducing agents include hydrosulfite, thiourea dioxide, zinc sulfoxylate formaldehyde, and sodium sulfoxylate formaldehyde.

[0154] <Chelating Agents> Examples of chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), gluconic acid, and hydroxyethylidenediphosphonic acid.

[0155] The method for manufacturing the deinked printed cloth 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 cloth obtained in the [deinking step].

[0156] [Washing Process] The washing process is a process of washing the deinked printed cloth obtained in the deinking process described above. Specifically, the washing process includes a water washing process in which the deinked printed cloth obtained in the deinking process described above is washed with water. The water washing process may be carried out while applying external force from the viewpoint of cleanliness. Examples of external force are the same as those exemplified in the deinking process. The amount of water used depends on the external force applied, but is preferably 5,000 to 50,000 parts by mass, more preferably 10,000 to 30,000 parts by mass, per 1 part by mass of printed cloth.

[0157] 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.

[0158] [Synthesis Example 1 of Deinking Adhesive] A glycol raw material composed of ethylene glycol, neopentyl glycol, and hexanediol in a weight ratio of 1:2:1 and a dicarboxylic acid raw material composed of isophthalic acid, adipic acid, and sebacic acid in a weight ratio of 22:5:9 were prepared. Next, in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 71.0 g of a polyol prepared by mixing the previously prepared dicarboxylic acid raw material with a molar ratio (OH / COOH) of hydroxyl groups of the glycol raw material to carboxylic acid groups of 1.11 was charged, along with 20.0 g of tolylene diisocyanate, 3.0 g of 1,4-butanediol, 6.0 g of 2,2'-dimethylolpropionic acid, and 53.7 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, 0.79 g of triethylamine and 404 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, under reduced pressure and a 40°C atmosphere, the solvent was removed by distillation to obtain deinking and fixing agent 1 (Tg: 8°C), which is a urethane resin, as an aqueous dispersion (solid content 23.0% by mass).

[0159] [Synthesis Example 2 of Deinking Adhesive] A glycol raw material composed of ethylene glycol, neopentyl glycol, and diethylene glycol in a weight ratio of 24:10:13 and a dicarboxylic acid raw material composed of terephthalic acid, phthalic anhydride, and adipic acid in a weight ratio of 5:22:14 were prepared. Next, in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 70.0 g of a polyol prepared by mixing the previously prepared dicarboxylic acid raw material with a molar ratio (OH / COOH) of hydroxyl groups of the glycol raw material to carboxylic acid groups of 1.17 was charged, along with 21.0 g of tolylene diisocyanate, 3.0 g of 1,4-butanediol, 6.0 g of 2,2'-dimethylolpropionic acid, and 53.7 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, 0.79 g of triethylamine and 404 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, under reduced pressure and a 40°C atmosphere, the solvent was removed by distillation to obtain deinking and fixing agent 2 (Tg: 26°C), which is a urethane resin, as an aqueous dispersion (solid content 25.0% by mass).

[0160] [Synthesis Example 3 of Deinking Adhesive] 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, in a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 74.0 g of polyol was mixed and reacted with the previously prepared dicarboxylic acid raw material at a molar ratio (OH / COOH) of hydroxyl groups of the glycol raw material to carboxylic acid groups of 1.19, and 20.0 g of isophorone diisocyanate, 6.0 g of 2,2'-dimethylolpropionic acid, and 53.7 g of methyl ethyl ketone were charged in these proportions, and the mixture was reacted under a nitrogen atmosphere at 75°C for 8 hours to obtain a urethane resin intermediate. Next, 3.15 g of 25% by mass aqueous ammonia solution and 404 g of ion-exchanged 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 3 (Tg: 55°C), which is a urethane resin, was obtained as an aqueous dispersion (solid content 22.4% by mass).

[0161] [Preparation of Binder Resin O-1] Binder resin O-1 (acrylic resin emulsion, DEXCEL CLEAR CONC F-7, manufactured by DIC Corporation, solids content 30.5% by mass) was prepared.

[0162] 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.

[0163] [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 number of mg of potassium hydroxide and measured according to JIS K 0070:1992. The results are shown in Table 1.

[0164] [Molecular Weight Measurement] 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 instrument (Tosoh Corporation "HLC-8220GPC") Column: The following columns from Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 ml. D. × 30 cm) × 1 TSKgel G4000 (7.8 ml. D. × 30 cm) × 1 TSKgel G3000 (7.8 ml. D. × 30 cm) × 1 TSKgel G2000 (7.8 ml. D. × 30 cm) × 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene. (Monodisperse polystyrene) Tosoh Corporation "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)

[0165] 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) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel-SuperAWN-H x 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: 10 mM LiBr DMF Flow rate: 0.6 mL / min Injection volume: 30 μL Standard samples: Calibration curves were prepared using the following monodisperse polystyrenes. (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)

[0166] [pH Measurement] pH was measured at 25°C using a pH meter (Horiba, Ltd.: pH meter F-71). The results are shown in Table 1.

[0167] [Tg Measurement] <Film Preparation> First, deinking and fixing agents 1 to 3, which are urethane resins, were diluted with deionized water to a non-volatile content of 10%, cast into a mold, and dried for 24 hours under conditions of 23°C and 65% RH to create a film with a thickness of 150 μm. <Tg Measurement> Next, 5 mg of the cut film was weighed into an aluminum open pan. Then, using a differential scanning calorimetry analyzer (device name "DSC Q-100", manufactured by TA Instruments Co., Ltd.), measurements were repeated twice under the conditions of a temperature range of -70 to 150°C, a heating rate of 10°C / min, and rapid cooling, and the glass transition temperature (Tg) obtained in the second measurement was adopted as the measured value.

[0168]

[0169] [Production of Deinking Agent (Deinking Agent Composition)] Deinking agent 1 (Deinking Agent Composition) was produced by mixing the basic compound, surfactant, and water shown in Table 2. The materials are as follows: ・Sodium hydroxide (Special grade sodium hydroxide, manufactured by Kishida Chemical Co., Ltd.) ・Polyoxyethylene styrylated phenyl ether (Neugen EA-137, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB = 13.0)

[0170]

[0171] [Preparation of base paste] The base paste was prepared by mixing a deinking binder with deionized water, a wetting agent, a thickener, a pH adjuster, and, if necessary, an instant binder for textile printing.

[0172] The details of each raw material of the base paste are as follows: Instant binder for printing: Binder resin O-1 (DEXCEL CLEAR CONC F-7, manufactured by DIC Corporation), acrylic resin emulsion Thickener: DEXCEL AGENT 15V, polyacrylic acid, manufactured by DIC Corporation, solids content: 88.0% pH adjuster: 25% ammonia water, manufactured by Wako Pure Chemical Industries Wetting agent: Propylene glycol, manufactured by Mitsubishi Chemical Corporation

[0173] (Examples 1-7, Comparative Example 1) [Production of Colored Adhesive Compositions] The prepared base adhesive was further mixed with the following pigment 1 and, if necessary, a crosslinking agent (silane coupling agent) to produce the colored adhesive compositions described in Tables 3 and 4. Pigment 1 is an aqueous pigment dispersion manufactured by DIC Corporation. Pigment 1: DEXCEL BLACK HR CONC, Pigment content: 40.0% by mass Crosslinking agent: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.

[0174] [Preparation of printed fabric for texture evaluation] Cotton satin (cotton satin, weight: 121 g / m2, Irozome Co., Ltd.) was stretched onto a bracket (chloroprene rubber, hardness 60, thickness 5 mm) and printed using a 135 mesh flat screen (24 cm x 32 cm solid pattern, 135 mesh, polyester screen, manufactured by Sanko Co., Ltd.) with a squeegee (chloroprene rubber, hardness 70, accessory for MH-5 type) using a test printing paste. This was then dried at 100°C for 1 minute using a dryer (Tsujii Dyeing Machine Industry Co., Ltd., MH-5 type), and then heat-treated at 150°C for 2 minutes using the same dryer (Tsujii Dyeing Machine Industry Co., Ltd., MH-5 type) to obtain printed fabric. From the 24 x 32 cm coated surface of the obtained printed fabric, a 20 cm x 20 cm section was cut using the common intersection of the diagonals to obtain printed fabric 1 for texture testing. Also, "cotton satin (weight: 121 g / m)" was used. ２ "T / C Broadcloth (T / C Broadcloth 65 / 35, Weight: 114g / m)" ２ Except for changing it to "Color Dyeing Company," the same procedure was followed to obtain a printed cloth 2 for texture testing.

[0175] [Texture Evaluation] The test stand clearance of the handle ometer (No. 226 Handle Ometer, manufactured by Yasuda Seisakusho) was adjusted to 20 mm, and the printed fabric 1 or 2 for texture testing was placed on the test stand with the printed surface facing upwards and parallel to the warp threads of the fabric so that the texture could be measured. The measurement range was set to 981 mN (100 gf), and the measurement time was 15 seconds. The measurement was repeated three times, and the average value obtained was adopted. A smaller value indicates a better texture.

[0176] [Preparation of dyed fabric for deinking test] Cotton satin (weight: 121 g / m)２ The fabric (from Irozome Co., Ltd.) was stretched onto a bracket (made of chloroprene rubber, hardness 60, thickness 5 mm), and 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) and test printing paste. This was then dried at 100°C for 1 minute using a dryer (manufactured by Tsujii Dyeing Machine Industry Co., Ltd., MH-5 type), and then heat-treated at 150°C for 2 minutes using the same dryer (manufactured by Tsujii Dyeing Machine Industry Co., Ltd., MH-5 type) to obtain a printed cloth. The obtained printed cloth was cut into a 3 cm x 5 cm rectangle so that the 2 cm x 4 cm rectangular pattern was in the center, and a deinking test printed cloth 1 with a white area and a printed area was obtained. The printed side of the test piece was used as the surface. Also, "cotton satin (weight: 121g / m)" ２ "T / C Broadcloth (T / C Broadcloth 65 / 35, Weight: 114g / m)" ２ Except for changing it to "Irozome Co., Ltd.", the same procedure was followed to obtain a printed cloth 2 for deinking testing.

[0177] [Evaluation of Deinking Properties] Five deinking test cloths 1 or 2, 20 iron balls (diameter: 6 mm), and 100 mL of deinking agent (200 parts by mass per 1 part by mass of test cloth) listed in Table 2 were placed in a stainless steel container attached to a rounder meter (L-16Z-T, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). Then, using the rounder meter, the cloths were treated at 40 revolutions per minute for 15 minutes under an atmosphere of 85°C, and then 10,000 mL of tap water was sprayed in a shower-like manner over each of the five deinking test cloths 1 or 2 to wash both sides. The evaluation criteria for deinking properties were as follows, and the surface of the deinking test cloths was evaluated. The evaluation criteria conformed to "JIS L 0804 2004, Grace Scale for Discoloration and Fading". A smaller value indicates more deinking and better deinking properties. The "JIS L 0804 2004, Grace Scale for Discoloration" uses a nine-level evaluation scale, but we have added "0" and "0-1" as evaluation criteria. "0" means that the printed area has returned to its original whiteness (deinked to its original whiteness), and "0-1" means a degree of deinking that falls between "0" and "1".

[0178]

[0179]

[0180] As shown in Table 3, it was confirmed that the printed fabric printed with the color paste composition of Example 1, which contains a urethane resin (deinkable adhesive 1) with a glass transition temperature (Tg) of 50°C or less, had better texture and deinkability compared to the printed fabric printed with the color paste composition of Comparative Example 1, which contains a urethane resin (deinkable adhesive 3) with a glass transition temperature (Tg) of more than 50°C.

[0181] As shown in Table 4, it was confirmed that the printed fabrics printed with the colored adhesive compositions of Examples 2 to 7, which contain a relatively high amount of urethane resin with a glass transition temperature (Tg) of 50°C or less, exhibited better deinking properties.

[0182] 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. A colored adhesive composition comprising a pigment and a deinking agent, wherein the deinking agent comprises a urethane resin (A1) having a glass transition temperature (Tg) of 50°C or less.

2. The colored paste composition according to claim 1, wherein the solid content of the deinking agent is 0.1% by mass or more and 40% by mass or less, based on the total amount of the colored paste composition.

3. A printed fabric that has been printed with the colored paste composition described in claim 1 or 2.

4. A method for producing a deinked printed fabric, comprising a deinking step of mixing the printed fabric described in claim 3, 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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