Pretreatment liquid for textile printing, ink set for textile printing, and textile printing method

Abstract

[Problem] To provide a pretreatment liquid for textile printing, an ink set for textile printing, and a textile printing method, capable of obtaining a printed matter having excellent washing fastness, good texture, and excellent image quality. [Solution] The pretreatment liquid for textile printing, etc., involve a quaternary ammonium cation having a formula weight of 100-300 and represented by formula (1), wherein the content of the quaternary ammonium cation represented by formula (1) is 5%-30% by mass based on the total amount of the pretreatment liquid for textile printing; and the pretreatment liquid or the like for textile printing is used before recording an image on fabric using textile printing ink including a pigment.

Description

Pretreatment liquid for textile printing, ink set for textile printing, and textile printing method

[0001] The present disclosure relates to a pretreatment liquid for textile printing, a textile printing ink set, and a textile printing method.

[0002] In recent years, various studies have been conducted on methods for printing on fabrics. For example, Japanese Patent Application Laid-Open No. 2020-105326 describes an ink set for inkjet printing, which includes an ink composition and a treatment liquid composition, wherein the treatment liquid composition contains a cationic compound and a compound having one quaternary ammonium group in its molecule, and the ink composition contains a pigment and an organic solvent, and the organic solvent contains a polyhydric alcohol solvent in an amount of 10.0% by mass or more and 55.0% by mass or less. JP 2021-70880 A describes a method for recording on fabric by ejecting a white ink composition for inkjet textile printing containing a white pigment and water using an inkjet recording device, in which the white ink composition is ejected as multiple droplets of 9 ng or less from the same nozzle, and by making the flight speed of the later ejected droplets faster than the flight speed of the earlier ejected droplets, the multiple droplets are ejected and recorded in such a way that they coalesce before landing on the fabric.

[0003] However, there are cases where it is required that the printed product obtained by printing on fabric has excellent washing fastness, good texture, and improved image quality.

[0004] The present disclosure has been made in view of the above circumstances, and an object of one embodiment of the present disclosure is to provide a textile printing pretreatment liquid, a textile printing ink set, and a textile printing method that are capable of producing printed textiles that are excellent in washing fastness, have a good texture, and have excellent image quality.

[0005] The present disclosure includes the following aspects: <1> A pretreatment liquid for textile printing, which contains a quaternary ammonium cation represented by the following formula (1) and has a formula weight of 100 to 300, the content of the quaternary ammonium cation represented by formula (1) being 5% by mass to 30% by mass based on the total amount of the pretreatment liquid for textile printing, and which is used before recording an image on a fabric using a pigment-containing textile printing ink. In formula (1), R １ and R ２ are groups having 10 or less carbon atoms. １ and R ２and each independently represent an unsubstituted alkyl group, a substituted alkyl group, a vinyl group, an aryl group, an allyl group, an alkyl ester group, a (meth)acryloyl group, or an amino group. <3> The pretreatment liquid for printing according to <1> or <2>, further comprising an alkanediol, the content of which is 3% by mass to 30% by mass based on the total amount of the pretreatment liquid for printing. <4> The pretreatment liquid for printing according to any one of <1> to <3>, wherein the quaternary ammonium cation represented by formula (1) is at least one selected from the group consisting of a diallyldimethylammonium cation, a (2-hydroxyethyl)trimethylammonium cation, and an N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation. <5> The textile printing pretreatment liquid according to any one of <1> to <4>, in which the quaternary ammonium cation represented by formula (1) has a formula weight of 100 to 200. <6> A textile printing ink set comprising the textile printing pretreatment liquid according to any one of <1> to <5>, and a textile printing ink containing a pigment. <7> The textile printing ink set according to <6>, in which the textile printing ink contains an alkanediol, and the content of the alkanediol is 3% by mass to 30% by mass relative to the total amount of the textile printing ink. <8> The textile printing ink set according to <6> or <7>, wherein at least one of the textile printing pretreatment liquid and the textile printing ink contains an alkanediol, and where the textile printing pretreatment liquid and the textile printing ink are of the same mass, the amount of available cations in the textile printing pretreatment liquid is A mmol / L, and the total content of the alkanediols contained in the textile printing pretreatment liquid and the textile printing ink is B mass%, the ratio of A to B is 15 or more. <9> The textile printing ink set according to any one of <6> to <8>, wherein the textile printing ink further contains an alkylene glycol alkyl ether, and the content of the alkylene glycol alkyl ether is 2 mass% to 20 mass% relative to the total amount of the textile printing ink. <10> The textile printing ink set according to any one of <6> to <9>, wherein the textile printing ink further contains urethane resin particles.<11> The textile printing ink set according to any one of <6> to <10>, wherein the pigment is dispersed by a polymer having a crosslinked structure. <12> A textile printing method comprising: a pretreatment liquid application step of applying a printing pretreatment liquid contained in the textile printing ink set according to any one of <6> to <11> to a fabric; and an ink application step of applying a printing ink contained in the textile printing ink set according to any one of <6> to <11> to the fabric to which the printing pretreatment liquid has been applied. <13> The textile printing method according to <12>, wherein the pretreatment liquid application step applies the printing pretreatment liquid by an inkjet recording method. <14> The textile printing method according to <13>, wherein the inkjet recording is performed in a single pass. <15> The textile printing method according to <12>, which comprises, after the ink application step, a step of heating the fabric to which the textile printing ink has been applied at a temperature of 100° C. or higher. <16> The textile printing method according to any one of <12> to <15>, which does not comprise, after the ink application step, a step of washing the fabric to which the textile printing ink has been applied. <17> The textile printing method according to any one of <12> to <16>, wherein the fabric is in a roll form and is made of cotton or a cotton-polyester blend.

[0006] According to an embodiment of the present disclosure, it is possible to provide a textile printing pretreatment liquid, a textile printing ink set, and a textile printing method that are capable of producing a printed textile that has excellent washing fastness, a good texture, and excellent image quality.

[0007] FIG. 1 is a diagram for explaining details of the evaluation criteria for image quality in the embodiment.

[0008] The textile printing pretreatment liquid, textile printing ink set, and textile printing method of the present disclosure will be described in detail below.

[0009] In this specification, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the examples.

[0010] As used herein, the amount of each component in a composition refers to the total amount of the components in the composition unless otherwise specified, when the composition contains multiple substances corresponding to each component. In this specification, a combination of two or more preferred aspects is a more preferred aspect. As used herein, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0011] [Pretreatment liquid for textile printing] The pretreatment liquid for textile printing (hereinafter also referred to as "pretreatment liquid") of the present disclosure contains a quaternary ammonium cation represented by the following formula (1) having a formula weight of 100 to 300. Hereinafter, the quaternary ammonium cation represented by formula (1) will also be referred to as "quaternary ammonium cation (1)." The content of the quaternary ammonium cation (1) is 5% by mass to 30% by mass with respect to the total amount of the pretreatment liquid. The pretreatment liquid of the present disclosure is for textile printing. Specifically, it is a pretreatment liquid used before recording an image on a fabric using a pigment-containing textile printing ink. That is, the pretreatment liquid and the textile printing ink are applied to the fabric in this order.

[0012] By applying the pretreatment liquid of the present disclosure to a fabric and then applying an ink to the fabric to which the pretreatment liquid has been applied, a printed item that has excellent washing fastness, good texture, and excellent image quality can be obtained.

[0013] Conventionally, a method has been known in which a pretreatment liquid containing a large amount of a cationic polymer is applied to a fabric in advance, but applying a pretreatment liquid containing a large amount of a cationic polymer to a fabric can result in a phenomenon in which the texture of the resulting printed textile is inferior.

[0014] If a pretreatment liquid contains a cationic polymer, the cationic polymer and the dispersant contained in the ink form a crosslinked structure on the fabric, which is thought to result in poor texture. In contrast, the pretreatment liquid of the present disclosure contains a quaternary ammonium cation (1) with a formula weight of 100 to 300, which is thought to result in excellent texture. In addition, the quaternary ammonium cation (1) causes the ink to aggregate, resulting in excellent washing fastness. Furthermore, the quaternary ammonium cation (1) has a formula weight of R １ and R ２ are all groups having 10 or less carbon atoms, R １ and R ２ Therefore, when a printing ink is applied onto the pretreatment layer formed by the pretreatment liquid, the printing ink spreads easily, which is thought to result in excellent image quality.

[0015] On the other hand, the pretreatment liquid described in JP 2020-105326 A contains a betaine compound, and there is no description focusing on the quaternary ammonium cation (1). １ and R ２ More than 10 quaternary ammonium cations were described, and the image quality was insufficient.

[0016] Each component contained in the pretreatment liquid of the present disclosure will be described below.

[0017] <Quaternary Ammonium Cation (1)> The pretreatment liquid contains a quaternary ammonium cation (1) having a formula weight of 100 to 300.

[0018] The formula weight of the quaternary ammonium cation (1) is 100 to 300, preferably 100 to 200. When the formula weight is 300 or less, a printed item with excellent texture can be obtained. When the formula weight is 100 or more, a printed item with excellent washing fastness can be obtained.

[0019] The formula weight can be calculated from the atomic weights of the atoms constituting the quaternary ammonium cation (1) by analyzing the structure of the quaternary ammonium cation contained in the pretreatment solution using a nuclear magnetic resonance (NMR) method.

[0020] The quaternary ammonium cation (1) is represented by the following formula (1).

[0021]

[0022] In formula (1), R １ and R ２ are all groups having 10 or less carbon atoms.

[0023] R in the quaternary ammonium cation (1) １ and R ２ and R １ and R ２ Therefore, when a printing ink is applied onto the pretreatment layer formed by the pretreatment liquid, the printing ink spreads easily, resulting in excellent image quality.

[0024] From the above perspective, R １ and R ２ The number of carbon atoms in the group is preferably 10 or less, more preferably 7 or less, and even more preferably 1 to 7.

[0025] Among them, R １ and R ２ are each preferably an unsubstituted alkyl group, a substituted alkyl group, a vinyl group, an aryl group, an allyl group, an alkyl ester group, a (meth)acryloyloxyalkyl group, or an amino group, more preferably an unsubstituted alkyl group, a substituted alkyl group, an allyl group, or a (meth)acryloyloxyalkyl group, and even more preferably an unsubstituted alkyl group, a substituted alkyl group, or an allyl group.

[0026] The unsubstituted alkyl group having 10 or less carbon atoms may be linear, branched, or cyclic. Of these, the unsubstituted alkyl group having 10 or less carbon atoms is preferably linear. The number of carbon atoms in the unsubstituted alkyl group is preferably 6 or less, more preferably 3 or less, and even more preferably 1 or 2.

[0027] The substituted alkyl group having 10 or less carbon atoms means an alkyl group having a substituent, and the number of carbon atoms including the substituent is 10 or less.

[0028] In the substituted alkyl group having 10 or less carbon atoms, the alkyl group may be linear, branched, or cyclic. In particular, in the substituted alkyl group having 10 or less carbon atoms, the alkyl group is preferably linear. The number of carbon atoms in the substituted alkyl group is preferably 6 or less, more preferably 3 or less, and even more preferably 1 or 2.

[0029] In the substituted alkyl group having 10 or less carbon atoms, examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and a (meth)acryloyl group. Among these, from the viewpoint of the storage stability of the pretreatment liquid, the substituent is preferably a hydroxy group, an aryl group, or a (meth)acryloyl group, and more preferably a hydroxy group.

[0030] The quaternary ammonium cation (1) is preferably contained in the pretreatment liquid as a quaternary ammonium salt. Examples of the counter anion in the quaternary ammonium salt include Cl. － ,Br － , I － halide ions such as those mentioned above; organic sulfonate anions having a substituent selected from an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aralkyl group, and a heterocyclic group; PF ６ － and B.F. ４ － From the viewpoint of solubility in the pretreatment solution, the counter anion is Cl. － ,Br － or a sulfonate anion having an alkyl group is preferred, and Cl － or Br － More preferably, Cl － is more preferable.

[0031] Among these, from the viewpoints of washing fastness, texture, and image quality, the quaternary ammonium cation (1) is preferably at least one selected from the group consisting of diallyldimethylammonium cation, (2-hydroxyethyl)trimethylammonium cation, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, and more preferably at least one selected from the group consisting of diallyldimethylammonium cation and (2-hydroxyethyl)trimethylammonium cation.

[0032] The content of the quaternary ammonium cation (1) is 5% by mass to 30% by mass, more preferably 8% by mass to 25% by mass, and even more preferably 10% by mass to 20% by mass, based on the total amount of the pretreatment liquid. When the content of the quaternary ammonium cation (1) is 5% by mass or more, a printed product with excellent image quality can be obtained. On the other hand, when the content of the quaternary ammonium cation is 30% by mass or less, a printed product with excellent texture can be obtained.

[0033] The content of the quaternary ammonium cation in the pretreatment liquid can be calculated, for example, by the following method.

[0034] First, if the pretreatment solution contains water and an aqueous organic solvent, as described below, they are removed by heat treatment or the like. Next, quaternary ammonium salts are extracted from the solid content contained in the pretreatment solution using GPC. The structure of the quaternary ammonium salt is analyzed using NMR, and the quaternary ammonium cations that make up the quaternary ammonium salts are identified. The amount of quaternary ammonium cations is calculated based on the amount of the extracted quaternary ammonium salt. The content of quaternary ammonium cations in the pretreatment solution is calculated based on the amount of the pretreatment solution and the amount of the quaternary ammonium salt.

[0035] (Water) The pretreatment liquid preferably contains water. The water content in the pretreatment liquid is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of the pretreatment liquid. The water content is preferably 98% by mass or less, more preferably 95% by mass or less, based on the total amount of the pretreatment liquid.

[0036] (Organic Solvent) The pretreatment liquid preferably contains at least one organic solvent.

[0037] Examples of the organic solvent include alcohol-based solvents, amide-based solvents, nitrile-based solvents, polyalkylene glycol-based solvents, and polyalkylene glycol alkyl ether-based solvents.

[0038] From the viewpoint of improving the ejection properties, it is preferable that the pretreatment liquid further contains an alkanediol. Examples of the alkanediol include 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and propylene glycol.

[0039] In particular, from the viewpoint of further improving the ejection properties, the alkanediol is preferably an alkanediol having 1 to 4 carbon atoms.

[0040] From the viewpoint of improving the ejection property, the proportion of the alkanediol in the organic solvent is preferably 90% by mass or more, more preferably 90% by mass or more. The upper limit of the proportion may be 100% by mass. From the viewpoint of further improving the ejection property, it is preferable that the organic solvent consists of only the alkanediol.

[0041] The content of the alkanediol is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass, relative to the total amount of the pretreatment liquid. When the content of the alkanediol is 3% by mass or more, the effect of improving the ejection properties is obtained. On the other hand, when the content of the alkanediol is 30% by mass or less, the ink is less likely to bleed, and image quality is improved.

[0042] The content of the organic solvent is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass, based on the total amount of the pretreatment liquid.

[0043] (Surfactant) The pretreatment liquid may contain at least one surfactant.

[0044] The surfactant is not particularly limited, and known surfactants such as silicone surfactants, fluorine surfactants, and acetylene glycol surfactants can be used.

[0045] When the pretreatment liquid according to the present disclosure contains a surfactant, the content of the surfactant is preferably 0.05% by mass to 2.0% by mass, and more preferably 0.1% by mass to 2.0% by mass, relative to the total amount of the pretreatment liquid.

[0046] (Other flocculants) The quaternary ammonium cation functions as a flocculant that aggregates the pigment in the ink. The pretreatment liquid may contain at least one flocculant other than the quaternary ammonium cation. Examples of other flocculants include polyvalent metal salts and cationic compounds.

[0047] Polyvalent Metal Salts Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Specific examples of polyvalent metal salts include calcium chloride, calcium nitrate, calcium sulfate, calcium acetate, calcium hydroxide, calcium carbonate, magnesium chloride, magnesium acetate, magnesium sulfate, magnesium carbonate, barium sulfate, barium chloride, zinc sulfide, zinc carbonate, and copper nitrate.

[0048] The cationic compound is not particularly limited and may be a low molecular weight compound or a high molecular weight compound. The cationic compound does not include the above-mentioned quaternary ammonium salts formed from a quaternary ammonium cation and a counter ion.

[0049] (Other Components) The pretreatment liquid may contain other components in addition to the above components, such as a pH adjuster, a fluorescent brightener, a surface tension adjuster, an antifoaming agent, an anti-drying agent, a lubricant, a thickener, an ultraviolet absorber, an anti-fading agent, an antistatic agent, a matting agent, an antioxidant, a resistivity adjuster, a rust inhibitor, an anti-reducing agent, an antiseptic, an anti-fungal agent, and a chelating agent.

[0050] [Textile Printing Ink Set] The textile printing ink set (hereinafter also referred to as "ink set") of the present disclosure includes the pretreatment liquid and a textile printing ink containing a pigment.

[0051] By applying the pretreatment liquid in the ink set of the present disclosure to a fabric and then applying the ink composition in the ink set of the present disclosure to the fabric to which the pretreatment liquid has been applied, it is possible to obtain a printed item that has excellent washing fastness, good texture, and excellent image quality.

[0052] <Ink> The ink contains at least one pigment.

[0053] The pigment may be either an organic pigment or an inorganic pigment that is normally commercially available. Examples of the pigment include those described in "Pigment Dictionary" edited by Seijiro Ito (published in 2000), "Industrial Organic Pigments" by W. Herbst and K. Hunger, and JP-A Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0054] The pigment may be a water-insoluble pigment that can be dispersed in water with the aid of a dispersant, or may be a self-dispersing pigment. A self-dispersing pigment is a pigment that can be dispersed in water without the use of a dispersant. A self-dispersing pigment is a compound in which at least one hydrophilic group selected from the group consisting of a carbonyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphate group, and salts thereof is chemically bonded to the surface of the pigment directly or via another group.

[0055] Examples of organic pigments include azo pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black. Examples of azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of polycyclic pigments include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. Examples of dye chelates include basic dye chelates and acid dye chelates.

[0056] Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.

[0057] From the viewpoints of image density and ink ejection properties, the content of the pigment in the ink is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1% by mass to 10% by mass, relative to the total amount of the ink.

[0058] (Water) The ink preferably contains water. The amount of water is not particularly limited, and is, for example, 40% to 70% by mass.

[0059] (Dispersant) The ink preferably contains a dispersant to disperse the pigment. The dispersant is not particularly limited as long as it is a polymer that can disperse the pigment, but from the viewpoint of dispersion stability, it preferably contains at least one hydrophilic group.

[0060] The dispersant may be a random copolymer or a block copolymer, and may have a crosslinked structure.

[0061] In particular, from the viewpoint of improving the ejection properties, it is preferable that the pigment is dispersed by a polymer containing a crosslinked structure.

[0062] When preparing the ink, a pigment dispersion in which a pigment is dispersed in water using a dispersant can also be used. Examples of the pigment aqueous dispersion include the pigment dispersion described in JP-A-2012-7148. Furthermore, commercially available pigment dispersions such as Pro-jet Black APD1000 (manufactured by Fujifilm Imaging Colorants) can also be used as pigment dispersions in which a pigment is dispersed in water using a polymer containing a crosslinked structure.

[0063] (Organic Solvent) The ink preferably contains at least one organic solvent.

[0064] Examples of the organic solvent include alcohol-based solvents, amide-based solvents, nitrile-based solvents, polyalkylene glycol-based solvents, and polyalkylene glycol alkyl ether-based solvents.

[0065] From the viewpoint of improving the ejection properties, it is preferable that the pretreatment liquid further contains an alkanediol.

[0066] In particular, from the viewpoint of further improving the ejection properties, the alkanediol is preferably an alkanediol having 1 to 4 carbon atoms.

[0067] The content of the alkanediol is preferably 3% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass, relative to the total amount of the pretreatment liquid. When the content of the alkanediol is 3% by mass or more, the effect of improving the ejection properties is obtained. On the other hand, when the content of the alkanediol is 30% by mass or less, the ink is less likely to bleed, and image quality is improved.

[0068] The pretreatment liquid preferably further contains an alkylene glycol alkyl ether.

[0069] Examples of alkylene glycol alkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.

[0070] From the viewpoint of improving abrasion resistance, the content of the alkylene glycol alkyl ether is preferably 2% by mass to 20% by mass relative to the total amount of the ink. When the content of the alkylene glycol alkyl ether is 2% by mass or more, the effect of improving abrasion resistance is obtained. On the other hand, when the content of the alkylene glycol alkyl ether is 20% by mass or less, both abrasion resistance and drying properties of the image can be achieved.

[0071] The content of the organic solvent is preferably 3% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, based on the total amount of the pretreatment liquid.

[0072] (Resin Particles) The ink preferably contains at least one type of resin particles.

[0073] The resin constituting the resin particles is preferably a water-insoluble resin. The term "water-insoluble" in the context of a water-insoluble resin means that the amount of the resin that dissolves in 100 g of distilled water at 25°C is less than 2 g.

[0074] The volume average particle size of the resin particles is preferably 1 nm to 300 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 150 nm.

[0075] In the present disclosure, the volume average particle size refers to a value measured using a laser diffraction / scattering particle size distribution analyzer. Examples of the measuring device include a particle size distribution analyzer "Microtrac MT-3300II" (manufactured by Nikkiso Co., Ltd.).

[0076] Examples of resin particles include urethane resin particles, acrylic resin particles, and ester resin particles.

[0077] For the resin particles, reference may be made to, for example, paragraphs 0038 to 0114 of International Publication No. 2021 / 192720 and paragraphs 0109 to 0120 of JP-A-2015-25076.

[0078] In particular, from the viewpoint of improving the texture of the printed textile, it is preferable that the ink contains urethane resin particles.

[0079] When the ink contains resin particles, the content of the resin particles is preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 15% by mass, relative to the total amount of the ink.

[0080] (Additives) The ink may contain additives such as surfactants, colloidal silica, co-sensitizers, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, and basic compounds, as needed.

[0081] (Relationship between Effective Cations and Alkanediols) At least one of the pretreatment liquid and the ink preferably contains an alkanediol, and from the viewpoint of ejection performance, it is more preferable that both the pretreatment liquid and the ink contain an alkanediol. However, as bleeding becomes more likely as the content of alkanediol increases, it is preferable to balance the content of alkanediol with the effective cations in the pretreatment liquid. Specifically, assuming that the pretreatment liquid and the ink have the same mass, the amount of effective cations in the pretreatment liquid is A mmol / L, and the total content of alkanediols contained in the pretreatment liquid and the ink is B mass %, it is preferable that the ratio of A to B (i.e., A / B) is 15 or greater.

[0082] The effective amount of cations is the value obtained by dividing the content of quaternary ammonium cation (1) contained in 1 liter of the pretreatment solution by the formula weight per cation of the quaternary ammonium cation (1).

[0083] From the viewpoint of further suppressing image bleeding, A / B is more preferably equal to or greater than 10. The upper limit of A / B is preferably 100 from the viewpoint of maintaining texture.

[0084] [Textile Printing Method] The textile printing method of the present disclosure preferably includes a pretreatment liquid application step of applying the pretreatment liquid contained in the ink set to a fabric, and an ink application step of applying the ink composition contained in the ink set to the fabric to which the pretreatment liquid has been applied.

[0085] The textile printing method of the present disclosure uses the ink set of the present disclosure, and therefore can produce printed textiles that are excellent in washing fastness, have a good texture, and have excellent image quality.

[0086] (Pretreatment Liquid Application Step) In the textile printing method of the present disclosure, first, a pretreatment liquid is applied to a fabric.

[0087] -Fabric- Examples of fiber types for fabrics include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers consisting of two or more types selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers.

[0088] The fiber in the fabric is preferably at least one selected from the group consisting of cotton and polyester. Examples of the fabric include woven fabric, knitted fabric, and nonwoven fabric. The fabric may be a fabric for fabric products.

[0089] In particular, the fabric is preferably in roll form and is made of cotton or a cotton-polyester blend.

[0090] Examples of fabric products include clothing (for example, T-shirts, sweatshirts, jerseys, pants, sweatsuits, dresses, blouses, etc.), bedding, and handkerchiefs.

[0091] - Application of Pretreatment Liquid - The method for applying the pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an inkjet method, a spray method, and a screen printing method. Among these, from the viewpoint of improving the texture of the resulting printed textile, the inkjet method is preferred as the method for applying the pretreatment liquid to the fabric. In other words, it is preferred to apply the pretreatment liquid using an inkjet recording method.

[0092] As the inkjet recording method, a commonly known method can be used, and examples thereof include a charge control method in which a pretreatment liquid is ejected by utilizing electrostatic attraction, a drop-on-demand method (pressure pulse method) in which the vibration pressure of a piezoelectric element is utilized, an acoustic inkjet method in which an electric signal is converted into an acoustic beam and the pretreatment liquid is irradiated with the acoustic beam, thereby ejecting the pretreatment liquid by utilizing radiation pressure, and a thermal inkjet method in which the pretreatment liquid is heated to form bubbles and the resulting pressure is utilized.

[0093] Generally, image recording methods using inkjet recording devices include a shuttle scan method (also known as a "serial head method"), which uses a short serial head to record an image, and a single-pass method (also known as a "line head method"), which uses a line head in which recording elements are arranged across the entire width of the recording medium. In the shuttle scan method, an image is recorded by scanning the serial head across the width of the recording medium. In contrast, in the single-pass method, an image can be recorded across the entire surface of the recording medium by scanning the recording medium in a direction perpendicular to the direction of the recording element arrangement. Therefore, unlike the shuttle scan method, the single-pass method does not require a transport system such as a carriage to scan the serial head. Furthermore, the single-pass method does not require complex scanning control of the carriage movement and the recording medium, and only the recording medium moves, allowing for faster recording speeds compared to the shuttle scan method.

[0094] The inkjet recording method is preferably performed in a single pass. According to the textile printing method of the present disclosure, even when performed in a single pass, it is possible to obtain a printed textile product that is excellent in washing fastness, has a good texture, and has excellent image quality.

[0095] The droplet volume of the pretreatment liquid ejected from the inkjet head is preferably 1 pL (picoliter) to 150 pL, more preferably 2 pL to 120 pL, and particularly preferably 20 pL to 60 pL. Note that the droplet volume refers to the volume of ink ejected from one nozzle at a time by the inkjet recording method.

[0096] The amount of the pretreatment liquid applied is 10 g / m from the viewpoint of texture. ２ ~30g / m２ It is preferable that the density is 15 g / m ２ ~25g / m ２ is.

[0097] The resolution for ejecting the pretreatment liquid is preferably 200 dpi (dots per inch) or more × 200 dpi or more, and more preferably 400 dpi or more × 400 dpi or more, and 1200 dpi or less × 1200 dpi or less. Here, "dpi" means the number of dots per 25.4 mm.

[0098] (Ink Application Step) In the textile printing method of the present disclosure, after the pretreatment liquid application step, the inks included in the ink set are applied to the fabric to which the pretreatment liquid has been applied.

[0099] - Application of ink - The method for applying the ink to the fabric to which the pretreatment liquid has been applied is not particularly limited, and examples thereof include a coating method, a padding method, an inkjet method, a spray method, and a screen printing method. Among these, the ink is preferably applied by an inkjet method from the viewpoint of improving the texture of the resulting printed textile. In other words, it is preferable to apply the ink composition using an inkjet recording method. The inkjet recording method is as described in the section on the pretreatment liquid application step.

[0100] The droplet volume of ink ejected from the inkjet head is preferably 1 pL (picoliter) to 150 pL, more preferably 2 pL to 120 pL, and particularly preferably 20 pL to 60 pL. Note that droplet volume refers to the volume of ink ejected from one nozzle at a time by the inkjet recording method.

[0101] The amount of ink applied is 10 g / m from the viewpoint of texture. ２ ~30g / m ２ It is preferable that the density is 15 g / m ２ ~25g / m ２ is.

[0102] The resolution in ink ejection is preferably 200 dpi or more×200 dpi or more, and more preferably 400 dpi or more×400 dpi or more, and 1200 dpi or less×1200 dpi or less.

[0103] (Heat Treatment Step) The textile printing method of the present disclosure preferably includes, after the ink application step, a step of heating the fabric to which the ink has been applied at a temperature of 100° C. or higher.

[0104] Examples of heat treatment devices include a heat drum, hot air, an infrared lamp, a heat oven, a heat plate, a heat press, and a hot plate. The heating temperature is preferably 100° C. to 180° C., and more preferably 120° C. to 170° C. The heating time is preferably 5 to 200 seconds, and more preferably 30 to 160 seconds.

[0105] The textile printing method of the present disclosure may include steps other than the steps described above. However, it is preferable that the method does not include a step of washing the fabric to which the ink has been applied after the ink application step. The textile printing method of the present disclosure is carried out using the pretreatment liquid and the ink. Since the pretreatment liquid contains the ammonium compound (1), the fixation of the pigment to the fabric is excellent, and there is no need to wash the fabric to which the ink has been applied.

[0106] Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples as long as it does not depart from the gist of the disclosure.

[0107] [Preparation of Pretreatment Liquid] A pretreatment liquid was prepared by mixing the following components and stirring for 60 minutes. Quaternary ammonium salt: quaternary ammonium salt shown in Tables 1 to 6...contents shown in Tables 1 to 6 Organic solvent: organic solvent shown in Tables 1 to 6...contents shown in Tables 1 to 6 Surfactant: product name "Olfine E1010", manufactured by Nissin Chemical Industry Co., Ltd....1.0% by mass Water...remaining amount to make the total pretreatment liquid 100% by mass

[0108] [Preparation of Ink] APD4000 Black (manufactured by Fujifilm Imaging Colorants Ltd.)... 4 mass% as pigment content Organic solvent: organic solvent listed in Tables 1 to 6...contents listed in Tables 1 to 3 Resin particles: resin particles listed in Tables 1 to 6...contents listed in Tables 1 to 6 Surfactant: product name "Olfine E1010", manufactured by Nissin Chemical Industry Co., Ltd.... 2.2 mass% Surfactant: product name "BYK345", manufactured by BYK... 0.1 mass% Polyvinylpyrrolidone: product name "PVPK15", manufactured by Tokyo Chemical Industry Co., Ltd.... 0.15 mass% Colloidal silica dispersion: product name "ST-XS", manufactured by Nissan Chemical Industries Co., Ltd.... 0.05 mass% as colloidal silica particle content Water... remaining amount to make the total ink 100 mass%

[0109] The ammonium salt and organic solvent used in preparing the pretreatment liquid, as well as the organic solvent and resin particles used in preparing the ink, are described below. Since a quaternary ammonium salt was used as a raw material when incorporating the quaternary ammonium cation (1) into the pretreatment liquid, details of the raw material are shown below. In the tables, components that were not included are marked with "-."

[0110] [Salts of quaternary ammonium cation (1)] DADMAC: diallyldimethylammonium chloride Choline chloride ABDMAC: N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium chloride Compound 1: didecyldimethylammonium chloride (product name "didecyldimethylammonium chloride", manufactured by Sigma-Aldrich)

[0111] [Cationic Compounds] The following compounds do not fall under the category of salts of quaternary ammonium cation (1): PolyDADMAC: diallyldimethylammonium chloride polymer (product name "PAS-H1L", manufactured by Nittobo Medical Co., Ltd.) Compound 2: lauryltrimethylammonium chloride (product name "Cortamin 24P", manufactured by Kao Corporation)

[0112] In Table 3, cationic compounds are also listed in the column for quaternary ammonium cations.

[0113] [Organic solvents] PG: Propylene glycol 1,2-BD: 1,2-butanediol 1,3-PD: 1,3-propanediol EG: Ethylene glycol DPGmME: Dipropylene glycol monomethyl ether

[0114] [Resin particles] Urethane A: Aqueous dispersion of urethane resin particles (product name "NeoRez R940", manufactured by Kusumoto Chemicals Co., Ltd.) Urethane B: Aqueous dispersion of urethane resin particles (product name "Superflex 460", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Urethane C: Aqueous dispersion of urethane resin particles (product name "Evaphanol HA-15", manufactured by Nicca Chemical Co., Ltd.) Styrene butadiene: Aqueous dispersion of styrene butadiene resin particles (product name "Rovene 4170", manufactured by Mallard Creek Polymers)

[0115] <Inkjet Textile Printing> Fabric was pretreated using the pretreatment liquid prepared in the Examples and Comparative Examples. The ink prepared in the Examples and Comparative Examples was applied to the pretreated fabric, followed by heat treatment to obtain a printed item. Details are as follows.

[0116] A long piece (15 cm x 4 cm) of 100% cotton fabric (product name "Cotton D5005" manufactured by Akahori Sangyo Co., Ltd.) was prepared as the fabric. An inkjet recording device equipped with an inkjet head (product name "StarFire SG-1024SA" manufactured by Fujifilm Dimatix) and an ink circulation pump was prepared. The fabric was fixed onto a stage as the recording medium. A pretreatment liquid and an ink composition were respectively filled into ink tanks connected to the inkjet head. The inkjet heads were arranged in a line with the nozzles aligned in a direction perpendicular to the direction of stage movement. The ejection conditions for the pretreatment liquid and ink were a droplet volume of 60 pL, an ejection frequency of 10 kHz, and a resolution of 400 dpi x 400 dpi. The ink circulation pump was operated to circulate the pretreatment liquid and ink between the ink tank and the inkjet head. First, the pretreatment liquid was ejected onto the entire surface of the recording medium to record a solid image. After drying with hot air at 60°C for 10 seconds, the ink was ejected to record an image, and a colored fabric was obtained. The colored fabric was then heat-treated at 160°C for 120 seconds using a heat press (automatic tabletop flat press AF-54TEN model, manufactured by Asahi Sen-i Kikai Co., Ltd.) to obtain a printed item.

[0117] <Evaluation> The above-mentioned printed textiles were used to carry out the following evaluations. The evaluation methods are as follows.

[0118] (Washing fastness) The printed fabric was evaluated based on B1S of ISO 105-C06:2010. If multiple evaluation criteria were met, the highest evaluation was adopted. AA: Both staining and discoloration were grades 4-5. A: Both staining and discoloration were grades 4 or higher. B: Both staining and discoloration were grades 3-4 or higher. C: Both staining and discoloration were grades 3 or higher. D: Either staining or discoloration was grade 2.

[0119] (Image Quality) The character images shown in Figure 1 were recorded at sizes of 10 pt, 12 pt, 14 pt, and 16 pt. The recorded character images were visually observed to evaluate the image quality. AA: No blurring of the character images was observed in all sizes of 10 pt, 12 pt, 14 pt, and 16 pt. A: No blurring of the character images was observed in sizes of 12 pt, 14 pt, and 16 pt, but some blurring was observed in the 10 pt size. B: No blurring of the character images was observed in sizes of 14 pt and 16 pt, but some blurring was observed in sizes of 10 pt and 12 pt. C: No blurring of the character images was observed in sizes of 18 pt, but some blurring was observed in sizes of 10 pt, 12 pt, and 14 pt. D: Blurring of the character images was observed in all sizes of 10 pt, 12 pt, 14 pt, and 16 pt.

[0120] (Feel) A rectangular evaluation sample with a length (long side) of 150 mm and a width (short side) of 50 mm was cut out from the obtained printed textile. A stainless steel plate with a length (long side) of 200 mm, a width (short side) of 100 mm, and a thickness of 1 mm was prepared as an evaluation jig. The evaluation jig was set upright with the short side oriented vertically and the long side oriented horizontally. Next, the center of the evaluation sample in the longitudinal direction (i.e., the center line) was placed on the long side of the horizontal evaluation jig, so that both longitudinal sides (both end sides) of the evaluation sample hung down. In this state, the linear distance between one longitudinal end and the other longitudinal end of the evaluation sample was measured, and the feel of the printed textile was evaluated based on the following evaluation criteria. In this evaluation, the softer the evaluation sample (i.e., the better the texture), the more both longitudinal ends of the evaluation sample sag under its own weight (i.e., the more the evaluation sample bends), and as a result, the linear distance between one longitudinal end and the other longitudinal end of the evaluation sample becomes shorter. AA: The linear distance is less than 40 mm. A: The linear distance is 40 mm or more and less than 55 mm. B: The linear distance is 55 mm or more and less than 70 mm. C: The linear distance is 70 mm or more and less than 85 mm. D: The linear distance is 85 mm or more.

[0121] (Abrasion resistance) The printed textile was evaluated based on ISO 105X12:2001 (wet). A: Grade 3-4 or higher B: Grade 3 C: Grade 2-3 D: Grade 2 or lower

[0122] The evaluation results are shown in Tables 1 to 6. In Table 6, compound 2 does not fall under the category of quaternary ammonium cation (1), but is a compound having R １ and R ２ The corresponding groups are shown.

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129] As shown in Tables 1 to 6, in Examples 1 to 23, a quaternary ammonium cation (1) having a formula weight of 100 to 300 was contained, and the content of the quaternary ammonium cation represented by formula (1) was 5% by mass to 30% by mass relative to the total amount of the pretreatment liquid. Therefore, printed products having excellent washing fastness, good texture, and excellent image quality could be obtained.

[0130] In Comparative Example 1, no quaternary ammonium cation (1) was contained, and it was found that the texture was poor. In Comparative Example 2, the content of quaternary ammonium cation (1) was more than 300, and it was found that the texture was poor. In Comparative Example 3, the quaternary ammonium cation contained a group having more than 10 carbon atoms, and it was found that the image quality was poor. In Comparative Example 4, the content of quaternary ammonium cation (1) was less than 5 mass%, and it was found that the image quality and texture were poor. In Comparative Example 5, the content of quaternary ammonium cation (1) was more than 30 mass%, and it was found that the texture was poor.

[0131] In Example 4, the content of alkanediol in the pre-treatment liquid was 3% by mass or more, and it was found to be superior in abrasion resistance compared to Example 8. In Example 3, the content of alkanediol in the pre-treatment liquid was 30% by mass or less, and it was found to be superior in image quality, texture, and abrasion resistance compared to Example 9.

[0132] In Example 21, the content of alkylene glycol alkyl ether in the ink was 2% by mass or more, and it was found to have superior abrasion resistance compared to Example 22. In Example 13, the content of alkylene glycol alkyl ether in the ink was 20% by mass or less, and it was found to have superior image quality and texture compared to Example 23.

[0133] In Examples 1, 11 and 12, the ink contained urethane resin particles, and it was found that the feel was superior to that of Example 10.

[0134] The disclosure of Japanese Patent Application No. 2023-168522, filed on September 28, 2023, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference.

Claims

1. A pretreatment liquid for textile printing, comprising a quaternary ammonium cation represented by the following formula (1) having a formula weight of 100 to 300, the content of the quaternary ammonium cation represented by the formula (1) being 5% by mass to 30% by mass based on the total amount of the pretreatment liquid for textile printing, the pretreatment liquid being used prior to image recording on a fabric with a pigment-containing printing ink. In formula (1), R １ and R ２ Each of the groups has 10 or less carbon atoms.

2. The above R １ and R ２ and each independently represent an unsubstituted alkyl group, a substituted alkyl group, a vinyl group, an aryl group, an allyl group, an alkyl ester group, a (meth)acryloyl group, or an amino group.

3. The pretreatment liquid for printing according to claim 1, further comprising an alkanediol, the content of which is 3% by mass to 30% by mass based on the total amount of the pretreatment liquid for printing.

4. The printing pretreatment liquid according to claim 1, wherein the quaternary ammonium cation represented by formula (1) is at least one selected from the group consisting of diallyldimethylammonium cation, (2-hydroxyethyl)trimethylammonium cation, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation.

5. The pretreatment liquid for textile printing according to claim 1, wherein the quaternary ammonium cation represented by formula (1) has a formula weight of 100 to 200.

6. A textile printing ink set comprising the textile printing pretreatment liquid according to any one of claims 1 to 5 and a textile printing ink containing a pigment.

7. The textile printing ink set according to claim 6, wherein the textile printing ink contains an alkanediol, and the content of the alkanediol is 3% by mass to 30% by mass relative to the total amount of the textile printing ink.

8. The textile printing ink set according to claim 6, wherein at least one of the printing pretreatment liquid and the printing ink contains an alkanediol, and wherein, assuming that the printing pretreatment liquid and the printing ink are of the same mass, an amount of available cations in the printing pretreatment liquid is A mmol / L, and a total content of the alkanediol contained in the printing pretreatment liquid and the printing ink is B mass %, a ratio of A to B is 15 or more.

9. The textile printing ink set according to claim 6, wherein the textile printing ink further contains an alkylene glycol alkyl ether, and the content of the alkylene glycol alkyl ether is 2% by mass to 20% by mass relative to the total amount of the textile printing ink.

10. The textile printing ink set according to claim 6, wherein the textile printing inks further contain urethane resin particles.

11. The textile printing ink set according to claim 6, wherein the pigment is dispersed by a polymer containing a crosslinked structure.

12. A textile printing method comprising: a pretreatment liquid application step of applying a printing pretreatment liquid contained in the textile printing ink set according to claim 6 to a fabric; and an ink application step of applying a textile printing ink contained in the textile printing ink set according to claim 6 to the fabric to which the printing pretreatment liquid has been applied.

13. The textile printing method according to claim 12, wherein in the pretreatment liquid application step, the printing pretreatment liquid is applied by an inkjet recording method.

14. The textile printing method according to claim 13, wherein the ink-jet recording method is performed in a single pass.

15. The textile printing method according to claim 12, further comprising a step of heating the fabric to which the textile printing ink has been applied at a temperature of 100° C. or higher after the ink application step.

16. The textile printing method according to claim 12, which does not include a step of washing the fabric to which the textile printing ink has been applied after the ink application step.

17. The textile printing method according to claim 12, wherein the fabric is in roll form and is made of cotton or a cotton-polyester blend.

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