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

Abstract

A color paste composition according to the present invention comprises a pigment and a silane coupling agent.

Description

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

[0001] The present invention relates to a color paste composition, a printed fabric, and a method for producing deinked printed fabric. This application claims priority from Japanese Patent Application No. 2024-102789, filed on June 26, 2024, the contents of which are incorporated herein by reference.

[0002] Advertising flags (nobori flags), which are rectangular pieces of fabric tied to a pole, are used as promotional tools in storefronts of various businesses, primarily restaurants. Advertising flags are printed with a color paste composition.

[0003] Patent Literature 1 discloses a pigment printing agent containing titanium oxide (B) and a polymer (A) obtained by polymerizing polymerizable monomers including a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having a hydrolyzable silyl group, wherein the polymer (A) alone produces a film with an elongation of 1,200 to 5,000% and a 1,000% modulus of 0.1 MPa or greater. It is disclosed that this pigment printing agent, even though it contains titanium oxide as a pigment, does not impair the original texture of the fabric when printed on the fabric, and exhibits excellent wash resistance, abrasion resistance, and the like of the printed area. Furthermore, the dye-overlay color area exhibits excellent wash resistance, making it possible to obtain printed fabrics with a natural texture and reduced color fading during washing, etc.

[0004] International Publication No. 2016 / 190208

[0005] The usage period of promotional flags is generally about half a month to half a year, and there is a problem that they are turned over quickly and the amount of waste is large. In recent years, environmental considerations have become more important, and there is a desire to recycle promotional flags. Therefore, from the perspective of recycling promotional flags, it is preferable that color paste compositions have excellent deinking properties. However, in conventional color paste compositions such as those described in Patent Document 1, the focus is on maintaining fastness against friction during wear and washing, and emphasis is placed on adhesion to fibers, so there is room for improvement in the deinking properties of color paste compositions.

[0006] The present invention has been made in view of the above circumstances, and has as its object to provide a color paste composition that has good washing resistance and abrasion resistance as well as good deinking properties, a printed fabric printed with the color paste composition, and a method for producing a deinked printed fabric obtained by deinking the printed fabric.

[0007] The present invention has the following aspects: [1] A color paste composition containing a pigment and a silane coupling agent. [2] The color paste composition according to [1], wherein the silane coupling agent contains a compound represented by the following general formula (i):

[0008] [In general formula (i), R ｉ１ , R ｉ２ , and R ｉ３ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one represents an alkoxy group having 1 to 10 carbon atoms; L ｉ１ represents a single bond or a spacer group, X ｉ１ represents an organic functional group.] [3] The color paste composition according to [1] or [2], wherein the content of the silane coupling agent is 0.1 to 5.0 mass % relative to the total amount of the color paste composition. [4] The color paste composition according to any one of [1] to [3], wherein the silane coupling agent contains two or more types of silane coupling agents. [5] The color paste composition according to any one of [1] to [4], further containing a crosslinking agent different from the silane coupling agent. [6] The color paste composition according to any one of [1] to [5], further containing a deinking fixing agent. [7] A printed fabric printed with the color paste composition according to any one of [1] to [6]. [8] A method for producing a deinked printed fabric, comprising a deinking step of mixing the printed fabric according to [7] with a deinking agent to obtain a deinked printed fabric.

[0009] According to the present invention, it is possible to provide a color paste composition that has good washing resistance and abrasion resistance as well as good deinking properties, a printed fabric printed with the color paste composition, and a method for producing a deinked printed fabric obtained by deinking the printed fabric.

[0010] (Color Paste Composition) The color paste composition of the present embodiment contains a pigment and a silane coupling agent.

[0011] <Pigment> The 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 even more preferably 30 to 45% by mass. The pigment may be a surface-treated pigment.

[0012] 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, red 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-chrome black, and copper-iron black; chromate pigments such as yellow lead and molybdate orange; ferrocyanide pigments such as iron blue; sulfide pigments such as cadmium yellow, cadmium red, zinc sulfide, and barium sulfide; ultramarine, calcium carbonate, cobalt violet, yellow iron oxide, and carbon black.

[0013] 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, 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.

[0014] 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).

[0015] The pigment and pigment dispersion may be used alone or in combination of two or more. The content of the pigment dispersion 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 color paste composition of this embodiment. The content of the pigment dispersion 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 color paste composition of this embodiment. Furthermore, the content of the pigment dispersion may be 7% by mass or less, or may be 5% by mass or less, based on the total amount of the color paste composition of this embodiment.

[0016] When the content of the pigment dispersion is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and rub resistance are further improved, and when the content of the pigment dispersion is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved.

[0017] 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 even more preferably 8% by mass or more and 12% by mass or less, relative to the total amount of the color paste composition of the present embodiment.

[0018] 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 color 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 color paste composition of this embodiment. Furthermore, the pigment content 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 this embodiment.

[0019] If the pigment content is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and rub resistance are further improved, and if the pigment content is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved.

[0020] 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 even 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 this embodiment. Furthermore, the content of the pigment may be 0.2% by mass or more and 4.2% by mass or less, based on the total amount of the color paste composition of this embodiment.

[0021] <Silane Coupling Agent> As the silane coupling agent, a compound represented by the following general formula (i) is preferred.

[0022] [In general formula (i), R ｉ１ , R ｉ２ , and R ｉ３ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one represents an alkoxy group having 1 to 10 carbon atoms; L ｉ１ represents a single bond or a spacer group, X ｉ１ represents an organic functional group.

[0023] R ｉ１ , R ｉ２ , and R ｉ３The alkyl group having 1 to 10 carbon atoms in the formula (I) 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.

[0024] The alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0025] R ｉ１ , R ｉ２ , and R ｉ３ The alkoxy group having 1 to 10 carbon atoms in the formula (I) 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.

[0026] The alkoxy group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0027] R ｉ１ , R ｉ２ , R ｉ３ Specific examples of the formula (R ｉ１／２／３ -1) to (R ｉ１／２／３ -11).

[0028] [Formula (R ｉ１／２／３ -1) to (R ｉ１／２／３ -11), the black dots represent bonds to the silicon atom (Si).

[0029] R ｉ１ , R ｉ２ , and R ｉ３ As the alkyl group having 1 to 10 carbon atoms in the above, from the viewpoint of steric hindrance around the Si atom, a linear alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred.

[0030] R ｉ１ , R ｉ２ , and R ｉ３ As the alkoxy group having 1 to 10 carbon atoms in the formula (I), from the viewpoint of hydrolysis property, a linear alkoxy group having 1 to 6 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is even more preferable.

[0031] R ｉ１ , R ｉ２ , and R ｉ３ Among the above, it is preferable that two or more of the groups be alkoxy groups having 1 to 10 carbon atoms, and it is more preferable that all of the groups be alkoxy groups having 1 to 10 carbon atoms.

[0032] L ｉ１ represents a single bond or a spacer group. The spacer group is a group having flexibility. More specifically, the spacer group represents an alkylene group having 1 to 15 carbon atoms. One or more —CH ２ Each - may be independently substituted with -O-. However, when the alkylene group is substituted with -O-, the oxygen atoms are not directly bonded to each other. The alkylene group is a linear, branched, or cyclic alkylene group, and is preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 6. L ｉ１ Specific examples of the alkylene group represented by the formula (L ｉ１ -1) to (L ｉ１ -4) and the like.

[0033] [Formula (L ｉ１ -1) to (L ｉ１ -4), the black dots represent bonds to silicon atoms (Si), and the white dots represent X ｉ１ represents a bond to .]

[0034] L ｉ１ From the viewpoint of affinity with resins and solvents, the above formula (L ｉ１ -2) ~ (L ｉ１ -4), or a single bond, and ｉ１ -2), a group represented by the above formula (L ｉ１ -3) or a single bond, and ｉ１ It is more preferable that the group is a group represented by the formula (3).

[0035] X ｉ１represents an organic functional group. The organic functional group is a functional group that is highly reactive with the binder resin.

[0036] Examples of the organic functional group include a group containing an epoxy group, a group containing an amino group, a group containing a mercapto group, a group containing a vinyl group, a group containing an isocyanate group, a group containing an amine group, a group containing an acrylic group, a group containing a methacrylic group, a group containing a urea group, and a group containing an imine group. The isocyanate group may have a blocked isocyanate structure protected with a protecting group. Examples of the protecting group include dimethylpyrazole, caprolactam, and ethanol.

[0037] X ｉ１ Specific examples of the formula (X ｉ１ -1) to (X ｉ１ -14a) and the like.

[0038] [Formula (X ｉ１ -1) to (X ｉ１ -14a) In the figure, the black dots are L ｉ１ represents a bond to .]

[0039] The above chemical formula (X ｉ１ More specifically, the group represented by the following chemical formula (X-14a) is ｉ１ -14-1) ~ (X ｉ１ -14-3).

[0040] [Formula (X ｉ１ -14-1) ~ (X ｉ１ -14-3) In the middle, the black dot is L ｉ１ represents a bond to .]

[0041] X ｉ１ From the viewpoint of compatibility with the binder resin, ｉ１ -1), a group represented by the above formula (X ｉ１ -3) to (X ｉ１ -5), a group represented by the above formula (X ｉ１ -10), a group represented by the above formula (X ｉ１ -13), or a group represented by the above formula (X ｉ１ -14-1), and the group represented by the above formula (X ｉ１-1), a group represented by the above formula (X ｉ１ -3), a group represented by the above formula (X ｉ１ -5), a group represented by the above formula (X ｉ１ -13), or a group represented by the above formula (X ｉ１ -14-1), and ｉ１ -1), or a group represented by the above formula (X ｉ１ -14-1) is more preferable.

[0042] Specific examples of the compound represented by general formula (i) include compounds represented by the following chemical formulas (i-1) to (i-25a).

[0043]

[0044] More specifically, the compound represented by the above chemical formula (i-25a) includes a compound represented by the following chemical formula (i-25).

[0045]

[0046] As the compound represented by general formula (i), among the above, the compound represented by the chemical formula (i-1), the compound represented by the chemical formula (i-2), the compound represented by the chemical formula (i-5), the compound represented by the chemical formula (i-10), the compound represented by the chemical formula (i-11), the compound represented by the chemical formula (i-15), the compound represented by the chemical formula (i-21), the compound represented by the chemical formula (i-23), and the compound represented by the chemical formula (i-25) are preferred, the compound represented by the chemical formula (i-1), the compound represented by the chemical formula (i-2), the compound represented by the chemical formula (i-15), the compound represented by the chemical formula (i-21), the compound represented by the chemical formula (i-23), and the compound represented by the chemical formula (i-25) are more preferred, and the compound represented by the chemical formula (i-1), the compound represented by the chemical formula (i-2), and the compound represented by the chemical formula (i-25) are even more preferred.

[0047] The silane coupling agent may be used alone or in combination of two or more. From the viewpoint of achieving both fastness and deinking property, the content of the silane coupling agent is preferably 0.1 to 5.0 mass%, more preferably 0.3 to 2.5 mass%, even more preferably 1.0 to 2.5 mass%, and particularly preferably 1.5 to 2.5 mass%, relative to the total amount of the color paste composition of this embodiment.

[0048] Furthermore, when two types of silane coupling agents are used 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 more preferably 60:40 to 40:60, from the viewpoint of achieving both fastness and deinking ability.

[0049] <Optional Components> The color paste composition of the present embodiment may contain optional components, such as a crosslinking agent other than the above-mentioned silane coupling agent, a deinking fixing agent, a binder resin, an organic solvent, a viscosity adjuster, a thickener, a pH adjuster, a wetting agent, a humectant, a flame retardant, and water.

[0050] <<Other Crosslinking Agents>> The color paste composition of this embodiment preferably contains a crosslinking agent other than the above-described silane coupling agent. Examples of other crosslinking agents include oxazoline-based compounds, isocyanate-based compounds, and carbodilite-based compounds. One or more of the other crosslinking agents may be used in combination. From the viewpoints of the texture of the fiber, the fastness of the printed textile, and the deinking ability, the content (solid content) of the other crosslinking agent 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.

[0051] When a silane coupling agent and another crosslinking agent are used in combination, the mass ratio of the silane coupling agent to the other crosslinking agent is preferably from 99:1 to 1:99, more preferably from 95:5 to 5:99, and even more preferably from 60:40 to 40:60, from the viewpoint of achieving both fastness and deinking ability.

[0052] <De-inking Fixing Agent> The color paste composition of this embodiment preferably contains a de-inking fixing agent. The de-inking fixing agent is a component that improves the fixability of the pigment in the color paste composition to the printed fabric, and is a component that is easily washed away during the de-inking process. The de-inking fixing agent is preferably an aqueous dispersion of a resin. The solids content of the de-inking fixing agent is preferably 10 to 55% by mass, preferably 15 to 50% by mass, and preferably 20 to 45% by mass.

[0053] The acid value of the deinking fixing agent is preferably 8 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.The acid value of the deinking fixing agent is preferably 45 mgKOH / g or less, more preferably 40 mgKOH / g or less, and even more preferably 30 mgKOH / g or less.

[0054] If the acid value of the deinking fixing agent is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and rub resistance will be further improved. If the acid value of the deinking fixing agent is equal to or less than the above-mentioned preferable upper limit, the deinking properties will be further improved.

[0055] For example, the acid value of the deinking fixing agent is preferably 8 mgKOH / g or more and 45 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less, and even more preferably 20 mgKOH / g or more and 30 mgKOH / g or less.

[0056] In this specification, the acid value is the amount of acid in 1 g of resin calculated by titrating the acid with an alkali, converted into mg of potassium hydroxide, and is a value measured in accordance with JIS K 0070:1992.

[0057] The pH of the deinking fixing agent is preferably 4 to 11, more preferably 5 to 10, and even more preferably 6 to 10, from the viewpoint of storage stability.

[0058] In this specification, pH refers to a value measured at 25° C. using a pH meter (manufactured by Horiba Ltd.: pH meter F-71).

[0059] The deinking fixing agent may be used alone or in combination of two or more. The content of the deinking fixing agent 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 color paste composition of this embodiment. Furthermore, the content of the deinking fixing agent as solids may be 1.5% by mass or more, or even 2% by mass or more, relative to the total amount of the color paste composition of this embodiment. The content of the deinking fixing agent 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 color paste composition of this embodiment. Furthermore, the content of the deinking fixing agent as solids 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 color paste composition of this embodiment.

[0060] If the content of the deinking fixing agent is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and abrasion resistance will be further improved. If the content of the deinking fixing agent is equal to or less than the above-mentioned preferable upper limit, the deinking property will be further improved.

[0061] For example, the content of the de-inking fixing agent as a solid content is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, even more preferably 0.5% by mass or more and 4% by mass or less, and particularly preferably 1% by mass or more and 4% by mass or less, relative to the total amount of the color paste composition of this embodiment.

[0062] When the deinking fixing agent is an aqueous dispersion of a urethane resin, the content of the solids (urethane resin) of the deinking fixing agent is preferably 0.1% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass, even more preferably 0.5% by mass to 4% by mass, and particularly preferably 1% by mass to 4% by mass. When the deinking fixing agent is an aqueous dispersion of an acrylic resin, the content of the solids (acrylic resin) of the deinking fixing agent is preferably 0.1% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass, even more preferably 0.5% by mass to 4% by mass, and particularly preferably 1% by mass to 4% by mass.

[0063] The mass ratio of the solid content of the deinking fixing agent which is a urethane resin to the solid content of the deinking fixing agent which is an acrylic resin [solid content of the deinking fixing agent which is a urethane resin / solid content of the deinking fixing agent which is an acrylic resin] 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.

[0064] Specific examples of deinking fixing agents include acrylic resins with a weight average molecular weight (Mw) of 100,000 or less, urethane resins with a weight average molecular weight (Mw) of 100,000 or less, and urethane resins with a weight average molecular weight (Mw) of more than 100,000.

[0065] [Acrylic resin having 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 a structural unit derived from styrene and a structural unit derived from an acrylic acid ester, acrylic acid, methacrylic acid, and / or acrylic acid amide. The styrene-acrylic resin preferably has a structural unit derived from methacrylic acid.

[0066] Examples of the acrylic acid ester include ethyl acrylate, normal butyl acrylate, etc. Examples of the acrylic acid amide include N-methylolacrylamide, etc.

[0067] 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.

[0068] When the weight average molecular weight (Mw) of the acrylic resin is 100,000 or less, the deinking properties of the color paste composition of this embodiment are improved. Also, when the weight average molecular weight (Mw) of the acrylic resin is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved. When the weight average molecular weight (Mw) of the acrylic resin is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and abrasion resistance are further improved.

[0069] The weight average molecular weight (Mw) of the acrylic resin is, for example, preferably 10,000 or more and 100,000 or less, more preferably 10,000 or more and 50,000 or less, still more preferably 14,000 or more and 40,000 or less, and particularly preferably 16,000 or more and 29,500 or less.

[0070] The weight-average molecular weight (Mw) of the acrylic resin means a value measured under the following conditions: When the acrylic resin was difficult to dissolve or not soluble at all, and a 10 mM LiBr DMF solution with a sample concentration of 0.4 mass % could not be prepared, the weight-average molecular weight (Mw) was deemed to be unmeasurable and to be greater than 100,000. Measurement equipment: High-speed GPC equipment ("HLC-8420GPC" manufactured by Tosoh Corporation) Column: One TSKgel-SuperAWN-H column manufactured by Tosoh Corporation, connected in series. 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% by mass) Standard sample: A calibration curve is prepared using the following monodisperse polystyrenes. (Monodisperse polystyrenes) "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-500" manufactured by Tosoh Corporation A-5000" Tosoh Corporation "TSKgel Standard Polystyrene F-1" Tosoh Corporation "TSKgel Standard Polystyrene F-2" Tosoh Corporation "TSKgel Standard Polystyrene F-4" Tosoh Corporation "TSKgel Standard Polystyrene F-10" Tosoh Corporation "TSKgel Standard Polystyrene F-20" Tosoh Corporation "TSKgel Standard Polystyrene F-40" Tosoh Corporation "TSKgel Standard Polystyrene F-80" Tosoh Corporation "TSKgel Standard Polystyrene F-128" Tosoh Corporation "TSKgel Standard Polystyrene F-288" Tosoh Corporation "TSKgel Standard Polystyrene F-550"

[0071] [Urethane Resin Having a Weight-Average Molecular Weight (Mw) of 100,000 or Less] The urethane resin having a weight-average molecular weight (Mw) of 100,000 or less preferably has a structural unit derived from a polyol compound, a structural unit derived from an isocyanate compound, and / or a structural unit derived from a hydroxycarboxylic acid compound.

[0072] Specific examples of the structural unit derived from a polyol compound include a structural unit derived from terephthalic acid, a structural unit derived from isophthalic acid, a structural unit derived from ethylene glycol, and a structural unit derived from diethylene glycol.

[0073] Specific examples of structural units derived from isocyanate compounds include structural units derived from isophorone diisocyanate, etc. Specific examples of structural units derived from hydroxycarboxylic acid compounds include structural units derived from 2,2'-dimethylolpropionic acid and structural units derived from 2,2'-dimethylolbutanoic acid.

[0074] 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.

[0075] When the weight average molecular weight (Mw) of the urethane resin is equal to or less than the above-mentioned preferable upper limit, the deinking property is further improved. When the weight average molecular weight (Mw) of the urethane resin is equal to or more than the above-mentioned preferable lower limit, the washing resistance and abrasion resistance are further improved.

[0076] The weight average molecular weight (Mw) of the urethane resin is, for example, preferably 10,000 or more and 100,000 or less, more preferably 10,000 or more and 80,000 or less, still more preferably 20,000 or more and 75,000 or less, and particularly preferably 30,000 or more and 65,000 or less.

[0077] The weight average molecular weight (Mw) of the urethane resin means a value measured under the following conditions. Measurement apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 mml.D. x 30 cm) x 1, TSKgel G4000 (7.8 mml.D. x 30 cm) x 1, TSKgel G3000 (7.8 mml.D. x 30 cm) x 1, TSKgel G2000 (7.8 mml.D. x 30 cm) x 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% by mass) Standard sample: A calibration curve was 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

[0078] [Urethane Resin Having a Weight-Average Molecular Weight (Mw) of More than 100,000] The urethane resin having a weight-average molecular weight (Mw) of more than 100,000 is preferably a urethane resin having a structural unit derived from a polyol compound, a structural unit derived from an isocyanate compound, a structural unit derived from a hydroxycarboxylic acid compound, and / or a structural unit derived from an amine compound.

[0079] Specific examples of the structural unit derived from a polyol compound include a structural unit derived from terephthalic acid, a structural unit derived from isophthalic acid, a structural unit derived from ethylene glycol, a structural unit derived from diethylene glycol, a structural unit derived from polypropylene glycol, and a structural unit derived from a polycarbonate diol (such as one derived from 1,6-hexanediol).

[0080] Specific examples of the structural unit derived from an isocyanate compound include a structural unit derived from isophorone diisocyanate, a structural unit derived from tolylene diisocyanate, and a structural unit derived from 4,4'-methylenebis(cyclohexyl isocyanate).

[0081] Specific examples of the structural unit derived from a hydroxycarboxylic acid compound include a structural unit derived from 2,2'-dimethylolpropionic acid and a structural unit derived from 2,2'-dimethylolbutanoic acid.

[0082] Examples of the structural unit derived from an amine compound include a structural unit derived from triethylamine, a structural unit derived from piperazine, and a structural unit derived from hydrazine.

[0083] The weight average molecular weight (Mw) of the urethane resin is preferably more 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.

[0084] When the weight average molecular weight (Mw) of the urethane resin is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and abrasion resistance are further improved. When the weight average molecular weight (Mw) of the urethane resin is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved.

[0085] The weight average molecular weight (Mw) of the urethane resin means a value measured under the following conditions. Measurement apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 mml.D. x 30 cm) x 1, TSKgel G4000 (7.8 mml.D. x 30 cm) x 1, TSKgel G3000 (7.8 mml.D. x 30 cm) x 1, TSKgel G2000 (7.8 mml.D. x 30 cm) x 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% by mass) Standard sample: A calibration curve was 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

[0086] <Binder Resin> The color paste composition of this embodiment preferably contains a binder resin. The binder resin is a resin having a weight-average molecular weight (Mw) of more than 100,000. However, the above-mentioned urethane resin is not included in the binder resin. The binder resin is preferably an acrylic resin emulsion. The weight-average molecular weight (Mw) of the acrylic resin means the value measured under the above-mentioned conditions. 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.

[0087] The acid value of the binder resin is preferably 8 mgKOH / g or more, more preferably 15 mgKOH / g or more, and is preferably 45 mgKOH / g or less, more preferably 40 mgKOH / g or less, and even more preferably 30 mgKOH / g or less.

[0088] When the acid value of the binder resin is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and rub resistance are further improved, and when the acid value of the binder resin is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved.

[0089] For example, the acid value of the binder resin is preferably 8 mgKOH / g or more and 45 mgKOH / g or less, more preferably 15 mgKOH / g or more and 40 mgKOH / g or less, and even more preferably 15 mgKOH / g or more and 30 mgKOH / g or less.

[0090] The pH of the binder resin is preferably 4 to 11, more preferably 4.5 to 11, even more preferably 5 to 10, and even more preferably 6 to 9, from the viewpoint of storage stability.

[0091] The binder resin may be used alone or in combination of two or more. The content of the binder resin as a solid content is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total amount of the color paste composition of this embodiment. The content of the binder resin as a solid content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on the total amount of the color paste composition of this embodiment.

[0092] If the solid content of the binder resin is equal to or greater than the above-mentioned preferable lower limit, the washing resistance and abrasion resistance are further improved. If the solid content of the binder resin is equal to or less than the above-mentioned preferable upper limit, the deinking properties are further improved.

[0093] For example, the content of the binder resin as a solid content 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 even more preferably 5% by mass or more and 10% by mass or less, relative to the total amount of the color paste composition of the present embodiment.

[0094] <Organic Solvent> Examples of the organic solvent include petroleum hydrocarbons and alcohols. One or more organic solvents may be used in combination. From the viewpoint of the sharpness of the printed textile, the content of the organic solvent is preferably 1.0 to 30.0 mass %, more preferably 5.0 to 25.0 mass %, and even more preferably 10.0 to 20.0 mass %, relative to the total amount of the color paste composition of this embodiment.

[0095] <Viscosity Adjuster> Examples of viscosity adjusters include stearic acid diesters, celluloses, polyvinyl alcohol, and organic bentonite. One or more viscosity adjusters may be used in combination. From the viewpoint of fastness of the printed textile, the content (solid content) of the viscosity adjuster is preferably 0.005 to 2.5 mass%, more preferably 0.010 to 1.5 mass%, and even more preferably 0.015 to 0.7 mass%, relative to the total amount of the color paste composition of this embodiment.

[0096] <Thickener> Examples of thickeners include polyacrylic acid, urethane-modified polyether, carboxymethyl cellulose, and xanthan gum. One or more types of thickeners may be used in combination. From the viewpoint of fastness of the printed textile, the content (solid content) of the thickener is preferably 0.008 to 1.0 mass%, more preferably 0.015 to 0.5 mass%, and even more preferably 0.02 to 0.1 mass%, relative to the total amount of the color paste composition of this embodiment.

[0097] <pH Adjuster> Examples of pH adjusters include ammonia, sodium hydroxide, potassium hydroxide, and organic amines. The pH adjuster may be used as is or as an aqueous solution. One or more pH adjusters may be used in combination. From the viewpoint of chemical resistance, the content of the pH adjuster 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 color paste composition of this embodiment.

[0098] <<Humectant>> Examples of humectants include monoethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin. One or more humectants may be used in combination. From the viewpoint of fastness of the printed textile, particularly washing resistance and wet rubbing fastness, 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.

[0099] <<Humectant>> Examples of humectants include urea, heparin, and petrolatum. One or more humectants may be used in combination. From the viewpoint of fastness of the printed textile, 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.

[0100] <Flame Retardant> Examples of the flame retardant include halogen-based flame retardants, phosphorus-based flame retardants, metal hydroxide-based flame retardants, and antimony-based flame retardants. One or more 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, relative to the total amount of the color paste composition of this embodiment.

[0101] <Water> Examples of water include ion-exchanged 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 textile printing workability, the content of water 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.

[0102] (Method for producing printed fabric and deinked printed fabric) The printed fabric of this embodiment is characterized by having been printed with the color paste composition described above. The printed fabric of this embodiment can be produced by a method for producing printed fabric comprising a printing step in which the color paste composition described above is printed onto fabric to obtain a printed fabric. The method for producing deinked printed fabric of this embodiment also comprises a deinking step in which the printed fabric is mixed with a deinking agent to obtain a deinked printed fabric. From the perspective of making deinking easier, a contact body may also be mixed in, and an external force may be applied by bringing the contact body into contact with the printed fabric.

[0103] [Printing Process] The printing process is a process of obtaining a printed fabric by printing the above-mentioned color paste composition onto a fabric. Examples of methods for printing the above-mentioned color paste composition onto a fabric include screen printing using a squeegee made of rubber, urethane resin, or the like, using a roller printing machine, flat screen printing machine, rotary screen printing machine, or the like. The screen used for screen printing is usually one with a mesh size of 60 to 300. After printing, a drying / heat treatment process is carried out at 100 to 150°C for 1 to 5 minutes to fix the color paste composition to the fabric.

[0104] As a method for printing the above-mentioned color paste composition onto a fabric, in addition to the above-mentioned screen printing, various printing methods can be used, such as gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, flow coating, etc. Furthermore, the above-mentioned color paste composition can also be applied to a fabric by immersion (padding method), spraying, or inkjet printing.

[0105] Examples of materials for the fabric include polyester, acrylic, polyethylene, polypropylene, nylon, cotton, vinylal, vinylon, ethylene vinyl alcohol fiber, polyvinyl chloride, vinylidene, modacrylic, acrylate, aramid, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyarylate fiber, polylactic acid, polyurethane, fluorine fiber, polyimide, polyether ester elastomer, polyphenylene sulfide, alginate, elastodien, elastolefin, melamine fiber, polycarbonamide, trivinyl, polybenzimidazole, chitin fiber, carbon fiber, glass fiber, metal fiber, ceramic fiber, rayon, polynosic, modal, lyocell, cupra, acetate, triacetate, promix, protein fiber, and blends thereof. The weight per unit area of ​​the polyester fabric is set to 40.0 to 120.0 g / m2, from the viewpoint that it is used as a fabric for general advertising flags. ２ is preferred, and 50.0 to 100.0 g / m ２ More preferably, 55.0 to 95.0 g / m ２ From the viewpoint of texture, the weight per unit area of ​​the cotton fabric is preferably 100 to 140 g / m ２ is preferred, and 105 to 135 g / m ２ More preferably, 110 to 130 g / m ２ The blended fibers of polyester and cotton include T / C broadcloth. From the viewpoint of texture, the weight per unit area of ​​T / C fabric is 95 to 135 g / m ２ is preferred, and 100 to 130 g / m ２ More preferably, 105 to 125 g / m ２The weight per unit area was calculated by measuring the weight of a piece of fabric cut into a square of 10 cm square using a balance and using the weight thus measured and the area of ​​the fabric.

[0106] [Deinking Step] The deinking step is a step in which the printed fabric is deinked in the presence of a deinking agent, if necessary, by applying an external force to the printed fabric, thereby obtaining a deinked printed fabric.

[0107] The amount of the deinking agent used is preferably 50 to 400 parts by mass, more preferably 75 to 300 parts by mass, per part by mass of the printed fabric.

[0108] The treatment temperature in the deinking step 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.

[0109] The treatment time in the deinking step is preferably 1 to 60 minutes, and more preferably 10 to 45 minutes.

[0110] The deinking step preferably involves a rotation process. Specifically, it is preferable to carry out a rotation process at 10 to 1000 rotations / minute, more preferably at 10 to 600 rotations / minute, and even more preferably at 10 to 100 rotations / minute.

[0111] The deinking step is preferably carried out using a stirrer. Examples of the stirrer include a rounder meter, a stirrer, an industrial washing machine, a bleaching / bleaching device, etc. Of these, a rounder meter and a stirrer are preferred as the stirrer.

[0112] A rounder meter is a device that rotates a container containing stainless steel balls, which stir the liquid. A stirrer is a device that uses magnetic force to rotate a magnetic rod called a rotor (stirrer) inside a container to stir the liquid.

[0113] When a rounder meter is used 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.

[0114] When a rounder meter is used in the deinking step, the number of stainless steel balls is preferably 5 to 45, and more preferably 10 to 30.

[0115] When a stirrer is used in the deinking process, the rotor is preferably tapered. The tapered shape specifications are preferably 10 mm - Φ4, 20 mm - Φ7, 25 mm - Φ8, or 30 mm - Φ8.

[0116] Among the above, the deinking step is preferably a step in which the above-mentioned deinking agent, a 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 preferably a step in which a deinked printed fabric is obtained by using a rounder meter, mixing the above-mentioned deinking agent, stainless steel balls, and the printed fabric in a container of the rounder meter, and bringing the stainless steel balls into contact with the printed fabric to apply an external force.

[0117] Applications of printed fabrics include advertising banners and curtains, clothing, sportswear, fashion items, bedding, household items such as interior furnishings, car seats, nonwoven fabrics, and the like.

[0118] <Deinking Agent> Examples of the deinking agent include a deinking agent containing a basic compound. The deinking agent may contain a surfactant, if necessary.

[0119] The pH of the deinking agent is preferably greater than 7 and equal to or less than 14, more preferably equal to or greater than 8 and equal to or less than 14, even more preferably equal to or greater than 10 and equal to or less than 14, and particularly preferably equal to or greater than 11 and equal to or less than 14. If the pH of the deinking agent is within the above range, the deinking properties will be further improved.

[0120] In this specification, pH refers to the value measured when the deinking agent is at 25°C using a pH meter (trade name: pH meter F-71, manufactured by Horiba, Ltd.).

[0121] <Basic Compound> Examples of the basic compound include basic inorganic compounds and basic organic compounds.

[0122] <Basic Inorganic Compounds> Examples of basic inorganic compounds include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal hydrogen carbonates, and the like. 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 hydrogen carbonates include sodium hydrogen carbonate and potassium hydrogen carbonate. Examples of alkali metal carbonates include sodium carbonate and potassium carbonate.

[0123] <Basic Organic Compound> Examples of the basic organic compound include amines, such as ammonia, pyridine, arginine, lysine, triethylamine, and triethanolamine.

[0124] Of the above, the basic compound is preferably a basic inorganic compound, more preferably an alkali metal hydroxide, and more preferably sodium hydroxide or potassium hydroxide.

[0125] 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.

[0126] When the content of the basic compound is equal to or greater than the above-mentioned preferable lower limit, the deinking property is further improved. When the content of the basic compound is equal to or less than the above-mentioned preferable upper limit, the influence on the printed fabric can be further reduced. Furthermore, the risk of the deinking composition as a chemical substance can be reduced, and recycling systems can be more easily adopted.

[0127] For example, the content of the basic compound 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 the deinking agent.

[0128] <Surfactant> The surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

[0129] The HLB value of the surfactant is preferably 1 or more and 18 or less, more preferably 3 or more and 17 or less, even more preferably 5 or more and 17 or less, and particularly preferably 6 or more and 17 or less.

[0130] When the HLB value of the surfactant is within the above preferred range, the deinking properties are further improved.

[0131] 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 determined experimentally by comparing the emulsifying power of various surfactants, but can typically be calculated using the following formula 1. Formula 1: HLB value = 20 x weight % of hydrophilic portion of surfactant / molecular weight of surfactant

[0132] Of the surfactants listed above, nonionic surfactants are preferred.

[0133] <Nonionic surfactants> Preferred nonionic surfactants are polyoxyalkylene alkyl ethers, polyoxyethylene styrylated phenyl ethers, and polyoxyalkylene tribenzyl phenyl ethers. Preferred polyoxyalkylene alkyl ethers include polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene tridecyl ether, polyoxyethylene polyoxypropylene branched decyl ether, and polyoxyethylene lauryl ether. Preferred polyoxyalkylene tribenzyl phenyl ethers include polyoxyethylene tribenzyl phenyl ether.

[0134] The HLB value of the polyoxyalkylene alkyl ether is preferably 1 or more and 15 or less, more preferably 3 or more and 14.5 or less, even more preferably 5 or more and 14 or less, and particularly preferably 6 or more and 10 or less.

[0135] The HLB value of the polyoxyethylene styrylated phenyl ether is preferably 1 or more and 18 or less, more preferably 10 or more and 17 or less, even more preferably 12 or more and 17 or less, and particularly preferably 13 or more and 16 or less.

[0136] Of the above, polyoxyethylene styryl phenyl ether is preferred as the nonionic surfactant.

[0137] The surfactant may be used alone or in combination of two or more. The content of the surfactant 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 content of the surfactant 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. Also, the content is preferably 0.1% by mass or less, and preferably 0.05% by mass or less, and the surfactant may not be included.

[0138] If the surfactant content is equal to or greater than the above-mentioned preferable lower limit, the deinking properties are further improved. If the surfactant content is equal to or less than the above-mentioned preferable upper limit, foaming is less likely to occur, making the paper easier to wash with water.

[0139] For example, the content of the surfactant 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.

[0140] The deinking agent may contain optional components other than the basic compound and surfactant described above. Examples of the optional components include water, a reducing agent, a chelating agent, and a flocculating agent.

[0141] <Water> Examples of water include ion-exchanged water, tap water, distilled water, etc. One type of water may be used alone, or two or more types may be used in combination.

[0142] 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, based on the total amount of the deinking agent.

[0143] <Reducing Agent> Examples of reducing agents include hydrosulfite, thiourea dioxide, zinc sulfoxylate-formaldehyde, and sodium sulfoxylate-formaldehyde.

[0144] <Chelating Agent> Examples of the chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), gluconic acid, and hydroxyethylidene diphosphonic acid.

[0145] The method for producing a deinked printed fabric of this embodiment may include an optional step other than the above-mentioned [deinking step]. Such optional step may include a washing step of washing the deinked printed fabric obtained in the [deinking step].

[0146] [Washing step] The washing step is a step in which the deinked printed fabric obtained in the deinking step described above is washed. Specific examples of the washing step include a water-washing step in which the deinked printed fabric obtained in the deinking step described above is washed with water. From the viewpoint of washability, the water-washing step may be carried out while applying an external force. Examples of external forces include the same external forces as those exemplified in the deinking step. The amount of water used depends on the external force applied, but is preferably 5,000 to 50,000 parts by mass, and more preferably 10,000 to 30,000 parts by mass, per part by mass of the printed fabric.

[0147] 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.

[0148] [Deinking Fixing Agent Synthesis Example 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, a four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 100 g of a polyol previously prepared by mixing and reacting the hydroxyl groups of the glycol raw material to the carboxylic acid groups of the dicarboxylic acid 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, and the mixture was reacted for 8 hours at 75°C under a nitrogen atmosphere to obtain a urethane resin intermediate. Next, 4.26 g of a 25% by weight aqueous ammonia solution and 546 g of ion-exchanged water were added to the urethane resin intermediate, and the mixture was stirred for 5 hours at 55°C under a nitrogen atmosphere to obtain an emulsion. The solvent was then distilled off under reduced pressure in an atmosphere of 40°C to obtain a deinking fixing agent 1, which was a urethane resin, as an aqueous dispersion (solid content 22.4% by mass).

[0149] [Synthesis Example 2 of Deinking Fixative] 200 g of ion-exchanged water, 9 g of DKS NL-180 polyoxyethylene lauryl ether, 8 g of DKS NL-450F polyoxyethylene lauryl ether, and 2 g of Hitenol LA-12 polyoxyethylene lauryl ether sulfate ester ammonium were thoroughly dissolved in a stainless steel container, and then 60 g of styrene monomer, 120 g of ethyl acrylate, 180 g of n-butyl acrylate, 50 g of methacrylic acid, and 5 g of n-dodecyl mercaptan were added and slowly emulsified to obtain an emulsion. Then, 300 g of ion-exchanged water, 3 g of DKS NL-180, and 20 g of isopropyl alcohol were placed in a stainless steel separable flask, and 0.5 g of ammonium persulfate, 0.8 g of sodium disulfite, and 0.3 g of a 1% aqueous solution of ferric chloride were added, and the mixture was heated to a 50°C atmosphere under a nitrogen reflux. Then, 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 were added dropwise from each nozzle of the flask and reacted for approximately 3 hours, thereby obtaining a deinking fixing agent 2, which is an acrylic resin, as an aqueous dispersion (solid content 41.0 mass%).

[0150] [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.

[0151] [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.

[0152] The types, acid values, molecular weights, and pH of the deinkable fixing agents and binder resins are shown in Table 1. The methods for measuring each parameter are as follows.

[0153] [Measurement of Acid Value] The amount of acid in 1 g of resin (deinking fixing agent or binder resin) calculated by titrating the acid with alkali was converted into mg of potassium hydroxide and measured according to JIS K 0070: 1992. The results are shown in Table 1.

[0154] [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 apparatus: High-speed GPC apparatus ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used: TSKgel G5000 (7.8 mml.D. x 30 cm) x 1 TSKgel G4000 (7.8 mml.D. x 30 cm) x 1 TSKgel G3000 (7.8 mml.D. x 30 cm) x 1 TSKgel G2000 (7.8 mml.D. x 30 cm) x 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% by mass) Standard sample: A calibration curve was 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

[0155] The weight average molecular weight (Mw) of the acrylic resin was measured under the following conditions, and the results are shown in Table 1. Measurement apparatus: High-speed GPC apparatus ("HLC-8420GPC" manufactured by Tosoh Corporation) Column: One TSKgel-SuperAWN-H column manufactured by Tosoh Corporation, connected in series. Detector: RI (differential refractometer) Column temperature: 40°C Eluent: 10 mM LiBr DMF Flow rate: 0.6 mL / min Injection volume: 30 μL Standard sample: A calibration curve was prepared using the following monodisperse polystyrenes. (Monodisperse polystyrenes) "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

[0156] [Measurement of pH] The pH was measured at 25° C. using a pH meter (manufactured by Horiba Ltd.: pH meter F-71). The results are shown in Table 1.

[0157]

[0158] [Preparation of base paste] Ion-exchanged water, a humectant, and a wetting agent were added to the instant binder for textile printing, and an organic solvent was added little by little to emulsify the mixture. A pH adjuster was then added and stirred, and finally a viscosity adjuster and a thickener were added to prepare the base paste.

[0159] Details of each raw material of the base glue are as follows: Instant binder 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 acrylic resin emulsions Moisturizing agent: Urea, manufactured by Mitsui Chemicals, Inc. Wetting agent: Monoethylene glycol, manufactured by Mitsubishi Chemical Corporation Organic solvent: Cactus Solvent P-20, petroleum hydrocarbon, manufactured by ENEOS Corporation pH adjuster: 25% ammonia water, manufactured by Wako Pure Chemical Industries, Ltd. Viscosity adjuster: DEXCEL AGENT E, manufactured by DIC Corporation, solid content: 42% by mass Thickener: DEXCEL AGENT 15V, polyacrylic acid, manufactured by DIC Corporation, solid content: 88.0%

[0160] (Examples 1 to 22, Comparative Example 1) [Production of Color Paste Composition] The prepared base paste was further mixed with the following silane coupling agents 1 to 7, the following pigments 1 to 4, and, if necessary, other crosslinking agents (DEXCEL AGENT GP CONC, oxazoline-based, manufactured by DIC Corporation, solid content: 28% by mass), and deinking fixing agents, to produce the color paste compositions shown in the tables.

[0161] Silane coupling agent 1: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-1) Silane coupling agent 2: KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-2) Silane coupling agent 3: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-5) Silane coupling agent 4: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-23) Silane coupling agent 5: KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-11) Silane coupling agent 6: KBE-9007N, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-21) Silane coupling agent 7: KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-10)

[0162]

[0163] Silane coupling agent 8: X-12-1308ES, manufactured by Shin-Etsu Chemical Co., Ltd., a compound represented by structural formula (i-25)

[0164]

[0165] Pigments 1 to 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

[0166] [Preparation of test printed fabric] Polyester tropical (SYC.T. Tropical white, weight: 89.5 g / m ２ A test piece was printed using a 135-mesh flat screen (2 cm x 4 cm rectangular pattern, 135 mesh, polyester screen, Sanko Co., Ltd.) and a squeegee (chloroprene rubber, hardness 70, accessory to the MH-5 model) with a test dyeing paste. The resulting fabric was dried at 100°C for 1 minute in a dryer (Tsujii Senki Kogyo Co., Ltd., MH-5 model) and then heat-treated at 150°C for 2 minutes in a dryer (Tsujii Senki Kogyo Co., Ltd., MH-5 model) to obtain a printed fabric. The resulting printed fabric was cut into a 3 cm x 5 cm rectangle with the 2 cm x 4 cm rectangular pattern in the center, yielding a test printed fabric with a white area and a printed area. The printed side of the test piece served as the front. In Example 20, "Polyester Tropical (SYC.T. Tropical White, Weight: 89.5 g / m ２ "Polyester pongee (T. Pongee HR, white, weight: 57.0 g / m, manufactured by Saiho Chemical Industry Co., Ltd.)" ２ The name was changed to "(manufactured by Saiho Chemical Industry Co., Ltd.)".

[0167] [Evaluation of deinking ability and white area staining] Five test printed fabrics, 20 iron balls (diameter: 6 mm), and 100 mL (200 parts by mass per part by mass of test printed fabric) of the deinking agent shown 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, treatment was carried out for 15 minutes at 40 rpm in an atmosphere of 85°C, and then 10,000 mL of tap water was sprayed like a shower onto the five test printed fabrics to rinse the front and back of the test printed fabrics. In Example 21, only the deinking agent and printed fabric were placed in a glass container (M-140IP, manufactured by Hakuyo Glass Co., Ltd.), and the test printed fabric was left to soak at 85°C for 15 minutes. After that, 10,000 mL of tap water was sprayed like a shower onto five pieces of test printed fabric, thereby rinsing both the front and back of the test printed fabric. The evaluation criteria for deinking ability were as follows, and the surfaces of the test printed fabrics were evaluated. The evaluation criteria were in accordance with "JIS L 0804 2004, Grace Scale for Discoloration and Fade." A smaller value indicates more deinking and better deinking ability. "JIS L 0804 2004, Grace Scale for Discoloration and Fade" is rated on a nine-point scale, but "0" and "0-1" were added 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 deinking degree between "0" and "1."

[0168] The evaluation criteria for white spot staining are as follows. The evaluation criteria conformed to "JIS L 0805 2005, Gray Scale for Staining." There are nine levels of evaluation, with a higher value indicating less white spot staining and less white spot staining. The results are shown in Tables 3 to 6.

[0169]

[0170] The sodium hydroxide in Table 2 is special grade sodium hydroxide manufactured by Kishida Chemical Co., Ltd., the polyoxyethylene polyoxypropylene lauryl ether is DKS NL-DASH 403 (HLB=6.5) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and the polyoxyethylene styrylated phenyl ether is Noigen EA-137 (HLB=13.0) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

[0171] [Laundry Fastness] The laundry fastness was measured in accordance with JIS L 0844:2011. Specifically, the laundry fastness was measured by placing five test printed fabrics in an accelerator (Laboratory Tester, LA-440, manufactured by Uenoyama Kiko Co., Ltd.), adding 100 mL of detergent water (a mixture of 200 g of Marcel needle soap (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), 80 g of sodium bicarbonate (manufactured by Tosoh Co., Ltd.), and 3,720 g of water). The test fabrics were then washed at 1,000 rpm for 5 minutes in a sealed space with a bellows-shaped cylinder surface. After the washing treatment, the test printed fabrics were removed and rinsed with 1,000 mL of tap water. The test printed fabrics were then dried at 50°C for 5 minutes using a heater, and the laundry fastness was then confirmed. The evaluation criteria were in accordance with JIS L 0804 2004, Grace Scale for Discoloration and Fading. The evaluation was made on a 9-point scale, with a higher value indicating stronger printing and better washing fastness. The results are shown in Tables 3 to 6.

[0172] [Rubbing Fastness (Dry) and Rubbing Fastness (Wet)] Rubbing fastness was measured in accordance with JIS L 0849:2013. Specifically, the test printed fabric was attached to a Gakushin-type rub fastness tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) using double-sided tape, cotton calico was attached to the jig, and 30 rectangular printed surfaces were rubbed with a force of 2 N for 3 minutes and 20 seconds, 100 times back and forth. The degree of color transfer and the degree of rubbing of the printed area were then confirmed. The wet rubbing test was performed by wetting the cotton calico with water and setting the pickup rate to 100%. The test printed fabric used was as follows: Polyester tropical (SYC.T. Tropical white, weight: 89.5 g / m ２The fabric was then ground onto a 135 mesh flat screen (2 cm x 4 cm rectangular pattern, 135 mesh, polyester screen, Sanko Co., Ltd.) and printed using a squeegee (chloroprene rubber, hardness 70, accessory to the MH-5 model) and a test dyeing paste. The fabric was then dried at 100°C for 1 minute using a dryer (Tsujii Senki Kogyo Co., Ltd., MH-5 model) and then heat-treated at 150°C for 2 minutes using a dryer (Tsujii Senki Kogyo Co., Ltd., MH-5 model) to obtain a printed fabric. The test printed fabric was then cut out so that 5 x 6 rectangular patterns of 2 cm x 4 cm remained on one sheet. In Example 20, "Polyester Tropical (SYC.T. Tropical White, weight: 89.5 g / m ２ "Polyester pongee (T. Pongee HR, white, weight: 57.0 g / m, manufactured by Saiho Chemical Industry Co., Ltd.)" ２ The evaluation criteria were based on "JIS L 0805 2005, Gray Scale for Staining." There are nine levels of evaluation, with higher values ​​indicating stronger printing and better rub fastness. The results are shown in Tables 3 to 6.

[0173]

[0174]

[0175]

[0176]

[0177] As shown in Tables 3 to 6, it was confirmed that the color paste compositions of Examples 1 to 22 had good washing resistance and abrasion resistance as well as good deinking properties compared to the color paste composition of Comparative Example 1 which did not contain a silane coupling agent.

[0178] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible within the scope of the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the appended claims.

Claims

1. It contains a pigment and a silane coupling agent. The silane coupling agent is a colored adhesive composition comprising a compound represented by the following general formula (i). 【Chemistry 1】 [In general formula (i), Ri1, Ri2, and Ri3 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, with at least one representing an alkoxy group having 1 to 10 carbon atoms; Li1 represents a single bond or a spacer group; and Xi1 represents a group represented by any of the following formulas: (Xi1-1), (Xi1-2), (Xi1-3), (Xi1-5), (Xi1-6), (Xi1-7), (Xi1-8), (Xi1-9), (Xi1-10), (Xi1-11), (Xi1-12), (Xi1-13), and (Xi1-14a).] 【Chemistry 2】 [In equations (X i1 -1), (X i1 -2), (X i1 -3), (X i1 -5), (X i1 -6), (X i1 -7), (X i1 -8), (X i1 -9), (X i1 -10), (X i1 -11), (X i1 -12), (X i1 -13), and (X i1 -14a), the black dots represent connections to Li1.]

2. The colored paste composition according to Claim 1, wherein the pigment content is 0.002% by mass or more with respect to the total amount of the colored paste composition.

3. The colored adhesive composition according to claim 1 or 2, wherein the content of the silane coupling agent is 0.1 to 5.0% by mass with respect to the total amount of the colored adhesive composition.

4. The colored adhesive composition according to claim 1 or 2, comprising two or more silane coupling agents.

5. Furthermore, the colored paste composition according to claim 1 or 2 contains a crosslinking agent different from the silane coupling agent.

6. Furthermore, the colored paste composition according to claim 1 or 2 contains a deinking adhesive.

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

8. A method for producing a deinked printed fabric, comprising a deinking step of mixing the printed fabric described in claim 7 with a deinking agent to obtain a deinked printed fabric.

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