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

Abstract

Provided are a pretreatment liquid for textile printing, an ink set for textile printing, and a textile printing method with which it is possible to obtain a printed article having excellent washing fastness, good texture, and excellent image quality. A pretreatment liquid for textile printing, which contains a quaternary ammonium cation represented by formula (1) in an amount of 100-300, and wherein the content of the quaternary ammonium cation represented by formula (1) is 5-30 mass% with respect to the total amount of the pretreatment liquid for textile printing, and which is used prior to image recording on a fabric using a textile printing ink containing a pigment.

Description

Technical Field

[0001] This invention relates to a pretreatment solution for printing and dyeing, a set of inks for printing and dyeing, and a printing and dyeing method. Background Technology

[0002] In recent years, various studies have been conducted on the printing and dyeing methods of fabrics.

[0003] For example, Japanese Patent Application Publication No. 2020-105326 discloses an ink kit for inkjet printing and dyeing, which comprises an ink composition and a processing liquid composition, wherein the processing liquid composition contains a cationic compound and a compound having one quaternary ammonium molecule, and the ink composition contains a pigment and an organic solvent, and the organic solvent contains 10.0% by mass and 55.0% by mass of a polyol solvent.

[0004] Japanese Patent Application Publication No. 2021-70880 discloses an inkjet recording method that uses an inkjet recording device to eject a white ink composition containing white pigment and water for inkjet printing and record it on a fabric. In the inkjet recording method, the white ink composition is ejected from the same nozzle as multiple droplets of 9 ng or less. Among the multiple droplets, the flight speed of the later ejected droplets is faster than that of the earlier ejected droplets. As a result, the multiple droplets are ejected and recorded in a combined manner before landing on the fabric. Summary of the Invention

[0005] The technical problem to be solved by the invention However, sometimes it is required that the printed materials obtained by dyeing fabrics have excellent wash fastness, good hand feel, and further improved image quality.

[0006] The present invention was made in view of this situation. One embodiment of the present invention aims to solve the problem of providing a pretreatment liquid for printing and dyeing, a set of printing and dyeing inks, and a printing and dyeing method for producing printed and dyed materials with excellent wash fastness, good hand feel, and excellent image quality.

[0007] means for solving technical problems The present invention includes the following methods.

[0008] <1> A pretreatment solution for printing and dyeing, comprising 100 to 300 of the following quaternary ammonium cation represented by formula (1), wherein, The content of quaternary ammonium cations, as expressed by formula (1), is 5% to 30% by mass relative to the total amount of the pretreatment solution used for dyeing and printing. The pretreatment solution for printing and dyeing is used before the fabric is imaged using printing and dyeing ink containing pigments.

[0009] [Chemical Formula 1] In equation (1), R 1 and R 2 All of them are groups with fewer than 10 carbon atoms.

[0010] <2> According to the pretreatment solution for printing and dyeing described in <1>, wherein, R 1 and R 2 It is a group having 10 or fewer carbon atoms and is independently an unsubstituted alkyl, substituted alkyl, vinyl, aryl, allyl, alkyl ester, (meth)acryloyl or amino group.

[0011] <3> According to <1> or <2>, the pretreatment solution for printing and dyeing further comprises alkanediol, wherein, The content of alkanediol is 3% to 30% by mass relative to the total amount of the pretreatment solution for printing and dyeing.

[0012] <4> The pretreatment solution for printing and dyeing according to any one of <1> to <3>, wherein, The quaternary ammonium cation represented by formula (1) is selected from at least one of diallyl dimethylammonium cation, (2-hydroxyethyl)trimethylammonium cation and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation.

[0013] <5> The pretreatment solution for printing and dyeing according to any one of <1> to <4>, wherein, The formula weight of the quaternary ammonium cation represented by formula (1) is 100 to 200.

[0014] <6> A printing and dyeing ink kit, comprising: The pretreatment solution for printing and dyeing as described in any one of <1> to <5>; and Printing inks containing pigments.

[0015] <7> According to the printing and dyeing ink kit described in <6>, wherein... Printing and dyeing inks contain alkanediols. The content of alkanediol is 3% to 30% by mass relative to the total amount of printing and dyeing ink.

[0016] <8> According to the printing and dyeing ink kit described in <6> or <7>, wherein, At least one of the pretreatment solution for printing and dyeing and the ink for printing and dyeing contains an alkanediol. The pretreatment solution and ink for printing and dyeing are set to the same quality. The effective cation concentration in the pretreatment solution for printing and dyeing is set as A mmol / L. Assuming the total content of alkanediols contained in the pretreatment solution and ink for printing and dyeing is set as B% by mass, The ratio of A to B is 15 or more.

[0017] <9> The printing and dyeing ink kit according to any one of <6> to <8>, wherein, Printing and dyeing inks also contain alkylene glycol alkyl ethers. The content of alkylene glycol alkyl ethers is 2% to 20% by mass relative to the total amount of printing and dyeing ink.

[0018] <10> According to any one of <6> to <9>, the ink kit for printing and dyeing, wherein, Printing and dyeing inks also contain urethane resin particles.

[0019] <11> The printing and dyeing ink kit according to any one of <6> to <10>, wherein, The pigment is dispersed in a polymer containing a cross-linked structure.

[0020] <12> A dyeing and printing method, comprising: The pretreatment liquid application step involves applying the pretreatment liquid for printing and dyeing included in any one of <6> to <11> of the printing and dyeing ink kit to the fabric; and In the ink application process, the ink for printing and dyeing included in any one of the ink kits for printing and dyeing (6) to (11) is applied to a fabric that has been treated with a pretreatment solution for printing and dyeing.

[0021] <13> According to the dyeing method described in <12>, wherein, In the pretreatment liquid application process, the pretreatment liquid for printing and dyeing is applied by inkjet recording.

[0022] <14> According to the dyeing method described in <13>, wherein, Inkjet recording is performed in a single-pass manner.

[0023] <15> The printing and dyeing method described in <12> includes: The process of heating the fabric that has been coated with printing ink at a temperature of 100°C or higher after the ink application process.

[0024] <16> The dyeing method according to any one of <12> to <15> does not include: The process of cleaning the fabric after the ink application process.

[0025] <17> The dyeing method according to any one of <12> to <16>, wherein, The fabric is rolled and is made of cotton or a cotton-polyester blend.

[0026] Invention Effects According to one embodiment of the present invention, a pretreatment solution for printing and dyeing, a set of printing and dyeing inks, and a printing and dyeing method can be provided to obtain printed and dyed materials with excellent wash fastness, good hand feel, and excellent image quality. Attached Figure Description

[0027] Figure 1 This is a diagram illustrating the detailed content of the image quality evaluation criteria in the embodiments. Detailed Implementation

[0028] The following provides a detailed description of the pretreatment liquid for printing and dyeing, the ink kit for printing and dyeing, and the printing and dyeing method of the present invention.

[0029] In this specification, the numerical range indicated by “~” refers to the range encompassed by taking the values ​​before and after “~” as the minimum and maximum values, respectively.

[0030] In the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the upper or lower limit of other numerical ranges described in different periods. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of a certain numerical range can be replaced with the values ​​shown in the embodiments.

[0031] In this specification, where multiple substances corresponding to each component are present in the composition, unless otherwise stated, the amount of each component in the composition represents the total amount of the multiple substances present in the composition.

[0032] In this specification, a combination of two or more preferred methods is a more preferred method.

[0033] In this specification, the term "process" includes not only independent processes, but also processes that can be clearly distinguished from other processes, as long as they achieve the desired purpose of the process.

[0034] [Pretreatment solution for printing and dyeing] The pretreatment solution for printing and dyeing of the present invention (hereinafter also referred to as "pretreatment solution") contains 100 to 300 of the quaternary ammonium cation represented by the following formula (1).

[0035] Hereinafter, the quaternary ammonium cation represented by formula (1) will also be referred to as "quaternary ammonium cation (1)".

[0036] The content of quaternary ammonium cation (1) was 5% to 30% by mass relative to the total amount of the pretreatment solution.

[0037] The pretreatment solution of the present invention is used for printing and dyeing. Specifically, it is a pretreatment solution used before recording an image on a fabric using printing and dyeing ink containing pigment. That is, the pretreatment solution and the printing and dyeing ink are applied to the fabric in sequence.

[0038] After applying the pretreatment liquid of the present invention to the fabric, if ink is applied to the fabric with the pretreatment liquid, a printed product with excellent wash fastness, good hand feel and excellent image quality can be obtained.

[0039] Previously, methods were known to pre-apply a pretreatment solution containing a large amount of cationic polymer to fabrics. However, when a pretreatment solution containing a large amount of cationic polymer is applied to fabrics, the resulting printed and dyed products sometimes have a poor hand feel.

[0040] If the pretreatment solution contains a cationic polymer, the cationic polymer and the dispersant contained in the ink will form a cross-linked structure on the fabric, resulting in a poor hand feel. In contrast, the pretreatment solution of the present invention contains a quaternary ammonium cation (1) with a formula weight of 100 to 300, resulting in an excellent hand feel.

[0041] Furthermore, the ink exhibits excellent wash fastness due to agglomeration via quaternary ammonium cations (1). Moreover, in the quaternary ammonium cations (1), R... 1 and R 2 All of them are groups with fewer than 10 carbon atoms, therefore R 1 and R 2 It will not become too hydrophobic. Therefore, it is believed that when printing ink is applied to the pretreatment layer formed by the pretreatment liquid, the printing ink spreads easily and the image quality is excellent.

[0042] On the other hand, the pretreatment solution described in Japanese Patent Application Publication No. 2020-105326 contains betaine compounds, but does not focus on the description of quaternary ammonium cations (1). The pretreatment solution described in Japanese Patent Application Publication No. 2021-70880 describes R... 1 and R 2 The image quality is unsatisfactory due to the presence of quaternary ammonium cations exceeding 10.

[0043] The components contained in the pretreatment solution of the present invention will be described below.

[0044] <Quaternary ammonium cation (1)> The pretreatment solution contains quaternary ammonium cations with a molecular weight of 100 to 300 (1).

[0045] 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, printed and dyed products with excellent hand feel can be obtained. Furthermore, when the formula weight is 100 or more, printed and dyed products with excellent wash fastness can be obtained.

[0046] Regarding the formula weight, the structure of the quaternary ammonium cation contained in the pretreatment solution can be analyzed using nuclear magnetic resonance (NMR) and calculated based on the atomic weight of the atoms constituting the quaternary ammonium cation (1).

[0047] The quaternary ammonium cation (1) is represented by the following formula (1).

[0048] [Chemical Formula 2] In equation (1), R 1 and R 2 All of them are groups with fewer than 10 carbon atoms.

[0049] If R in quaternary ammonium cation (1) 1 and R 2 If all carbon atoms are less than 10, then R 1 and R 2 It will not become too hydrophobic. Therefore, when printing ink is applied to the pretreatment layer formed by the pretreatment liquid, the printing ink spreads easily and the image quality is excellent.

[0050] Based on the above viewpoints, R 1 and R 2 The number of carbon atoms is preferably 10 or less, more preferably 7 or less, and even more preferably 1 to 7.

[0051] Among them, R 1 and R 2 Preferably, the group has 10 or fewer carbon atoms and is independently unsubstituted alkyl, substituted alkyl, vinyl, aryl, allyl, alkyl ester, (meth)acryloyloxyalkyl or amino, more preferably unsubstituted alkyl, substituted alkyl, allyl or (meth)acryloyloxyalkyl, and even more preferably unsubstituted alkyl, substituted alkyl or allyl.

[0052] The unsubstituted alkyl group having 10 or fewer carbon atoms can be linear, branched, or cyclic. Preferably, the unsubstituted alkyl group having 10 or fewer carbon atoms is linear. The unsubstituted alkyl group preferably has 6 or fewer carbon atoms, more preferably 3 or fewer, and even more preferably 1 or 2.

[0053] Substituted alkyl groups with 10 or fewer carbon atoms refer to alkyl groups having substituents and having 10 or fewer carbon atoms including the substituents.

[0054] Among the substituted alkyl groups with 10 or fewer carbon atoms, the alkyl group can be straight-chain, branched, or cyclic. Preferably, the alkyl group is straight-chain. The substituted alkyl group preferably has 6 or fewer carbon atoms, more preferably 3 or fewer, and even more preferably 1 or 2.

[0055] Among substituted alkyl groups with 10 or fewer carbon atoms, examples of substituents include hydroxyl, carboxyl, alkyl, aryl, heteroaryl, alkoxy, aryloxy, heteroaryloxy, alkyl thioether, aryl thioether, heteroaryl thioether, and (meth)acryloyl.

[0056] From the viewpoint of the preservation stability of the pretreatment solution, the substituent is preferably hydroxyl, aryl, or (meth)acryloyl, and more preferably hydroxyl.

[0057] The preferred quaternary ammonium cation (1) is contained in the pretreatment solution as a quaternary ammonium salt. Examples of counterions in the quaternary ammonium salt include Cl-. - ,Br - I - Isohalide ions; organic sulfonic acid anions having substituents selected from alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aralkyl, and heterocyclic groups; PF6 - and BF4 - From the viewpoint of solubility in the pretreatment solution, the preferred counterion is Cl. - ,Br - Or a sulfonic acid anion containing an alkyl group, more preferably Cl - or Br - Cl is further preferred. - .

[0058] From the viewpoints of wash fastness, feel and image quality, the quaternary ammonium cation (1) is preferably selected from at least one of diallyl dimethylammonium cation, (2-hydroxyethyl)trimethylammonium cation and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, and more preferably from at least one of diallyl dimethylammonium cation and (2-hydroxyethyl)trimethylammonium cation.

[0059] The content of quaternary ammonium cation (1) relative to the total amount of the pretreatment solution is 5% to 30% by mass, more preferably 8% to 25% by mass, and even more preferably 10% to 20% by mass. If the content of quaternary ammonium cation (1) is 5% by mass or more, a printed product with excellent image quality can be obtained. On the other hand, if the content of quaternary ammonium cation is 30% by mass or less, a printed product with excellent hand feel can be obtained.

[0060] The content of quaternary ammonium cations in the pretreatment solution can be calculated, for example, by the following method.

[0061] First, if the pretreatment solution contains water and aqueous organic solvents (described later), these are removed by heat treatment or the like. Next, quaternary ammonium salts are extracted from the solid components contained in the pretreatment solution using GPC. The structure of the quaternary ammonium salt is analyzed using NMR, and the quaternary ammonium cations constituting the quaternary ammonium salt are identified. The amount of quaternary ammonium cations is calculated based on the amount of extracted quaternary ammonium salt. The content of quaternary ammonium cations in the pretreatment solution is calculated based on the amount of pretreatment solution and the amount of quaternary ammonium salt.

[0062] (water) The pretreatment solution preferably contains water. The water content in the pretreatment solution is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total amount of the pretreatment solution. Furthermore, the water content is preferably 98% by mass or less, more preferably 95% by mass or less, relative to the total amount of the pretreatment solution.

[0063] (Organic solvent) The pretreatment solution preferably contains at least one organic solvent.

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

[0065] From the viewpoint of improving dischargeability, the pretreatment solution preferably also contains alkanediol.

[0066] Examples of alkanediols 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.

[0067] From the perspective of further improving excretion, alkanediols are preferably alkanediols with 1 to 4 carbon atoms.

[0068] From the viewpoint of improving emissions, the proportion of alkanediol in the organic solvent is preferably 90% by mass or more, more preferably 90% by mass or more. The upper limit of the above proportion can be 100% by mass.

[0069] From the perspective of further improving dischargeability, organic solvents are preferably composed of only alkyl diols.

[0070] The content of alkanediol relative to the total amount of the pretreatment liquid is preferably 3% to 30% by mass, more preferably 5% to 20% by mass. If the content of alkanediol is 3% by mass or more, the effect of improved extrudability can be obtained. On the other hand, if the content of alkanediol is 30% by mass or less, the ink is less prone to bleeding, and the image quality is improved.

[0071] The content of organic solvent relative to the total amount of pretreatment liquid is preferably 3% to 30% by mass, more preferably 5% to 20% by mass.

[0072] (surfactant) The pretreatment solution may contain at least one surfactant.

[0073] There are no particular restrictions on the use of surfactants; known surfactants such as silicone surfactants, fluorinated surfactants, and acetylene glycol surfactants can be used.

[0074] When the pretreatment solution of the present invention contains a surfactant, the content of the surfactant relative to the total amount of the pretreatment solution is preferably 0.05% to 2.0% by mass, more preferably 0.1% to 2.0% by mass.

[0075] (Other flocculants) Quaternary ammonium cations act as coagulants to agglomerate pigments in inks. The pretreatment solution may contain at least one coagulant other than quaternary ammonium cations. Examples of other coagulants include polyvalent metal salts and cationic compounds.

[0076] -Polyvalent metal salts- Polyvalent metal salts are compounds composed of metal ions and anions with a valence of divalent or higher. Specifically, 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.

[0077] -Catonic compounds- There are no particular limitations on whether it is a cationic compound or a high molecular weight compound. The cationic compound does not contain quaternary ammonium salts composed of the aforementioned quaternary ammonium cations and counterions.

[0078] (Other ingredients) The pretreatment solution may contain other components besides those mentioned above. Examples of such other components include, for instance, pH adjusters, fluorescent whitening agents, surface tension modifiers, defoamers, anti-drying agents, lubricants, thickeners, UV absorbers, anti-fading agents, antistatic agents, matting agents, antioxidants, resistivity modifiers, rust inhibitors, reduction inhibitors, preservatives, fungicides, and chelating agents.

[0079] [Ink Kit for Printing and Dyeing] The printing and dyeing ink kit of the present invention (hereinafter also referred to as "ink kit") comprises the above-mentioned pretreatment liquid and printing and dyeing ink containing pigment.

[0080] After applying the pretreatment liquid from the ink kit of the present invention to the fabric, if the ink composition from the ink kit of the present invention is applied to the fabric that has been pretreated, a printed fabric with excellent wash fastness, good hand feel and excellent image quality can be obtained.

[0081] <Ink> The ink contains at least one pigment.

[0082] Pigments can be either commercially available organic or inorganic pigments. Examples of pigments include, for instance, those described in Seishiro Itō's "Encyclopedia of Pigments" (2000), W. Herbst, K. Hunger's "Industrial Organic Pigments," Japanese Patent Application Publication Nos. 2002-12607, 2002-188025, 2003-26978, and 2003-342503.

[0083] Furthermore, the pigment can be a water-insoluble pigment that can be dispersed in water by a dispersant, or it can be a self-dispersible pigment. A self-dispersible pigment is a pigment that can be dispersed in water even without the use of a dispersant. For example, a self-dispersible pigment is a compound formed by direct or chemical bonding to the surface of the pigment via other groups, consisting of at least one hydrophilic group selected from carbonyl, hydroxyl, carboxyl, sulfonyl, phosphate, and their salts.

[0084] 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 chelated azo pigments. Examples of polycyclic pigments include phthalocyanine pigments, perylene pigments, perylene ketone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindolinone pigments, isoindolineone pigments, and quinophthalone pigments. Examples of dye chelates include basic dye-type chelates and acidic dye-type chelates.

[0085] Examples of inorganic pigments include titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black.

[0086] From the viewpoint of image density and ink dischargeability, the pigment content in the ink is preferably 1% to 20% by mass relative to the total amount of ink, more preferably 1% to 15% by mass, and even more preferably 1% to 10% by mass.

[0087] (water) The ink preferably contains water. The water content is not particularly limited, for example, it can be 40% to 70% by mass.

[0088] (Dispersant) To disperse the pigment, the ink preferably contains a dispersant. The dispersant is not particularly limited as long as it is a polymer capable of dispersing the pigment, but from the viewpoint of dispersion stability, it is preferable to contain at least one hydrophilic group.

[0089] The dispersant can be a random copolymer or a block copolymer.

[0090] Dispersants can also have cross-linked structures.

[0091] From the viewpoint of improving dischargeability, pigments are preferably dispersed in polymers containing cross-linked structures.

[0092] When preparing inks, pigment dispersions in water, which utilize dispersants to disperse pigments, can also be used. For example, the pigment dispersion described in Japanese Patent Application Publication No. 2012-7148 can be used as a pigment dispersion. Furthermore, commercially available products such as Pro-jet BlackAPD1000 (manufactured by Fujifilm Imaging Colorants, Inc.) can also be used as pigment dispersions in water using polymers containing cross-linked structures.

[0093] (Organic solvent) The ink preferably contains at least one organic solvent.

[0094] Examples of organic solvents include alcohol solvents, amide solvents, nitrile solvents, polyalkylene glycol solvents, and polyalkylene glycol alkyl ether solvents.

[0095] From the viewpoint of improving dischargeability, the pretreatment solution preferably also contains alkanediol.

[0096] From the perspective of further improving excretion, alkanediols are preferably alkanediols with 1 to 4 carbon atoms.

[0097] The content of alkanediol relative to the total amount of the pretreatment liquid is preferably 3% to 30% by mass, more preferably 5% to 20% by mass. If the content of alkanediol is 3% by mass or more, the effect of improved extrudability can be obtained. On the other hand, if the content of alkanediol is 30% by mass or less, the ink is less prone to bleeding, and the image quality is improved.

[0098] The pretreatment solution preferably also contains alkylene glycol alkyl ethers.

[0099] Examples of alkylene glycol alkyl ethers include, for example, 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.

[0100] From the viewpoint of improving abrasion resistance, the content of alkylene glycol alkyl ethers is preferably 2% to 20% by mass relative to the total amount of ink.

[0101] If the content of alkylene glycol alkyl ethers is 2% by mass or more, the abrasion resistance can be improved. On the other hand, if the content of alkylene glycol alkyl ethers is 20% by mass or less, both abrasion resistance and image drying properties can be achieved.

[0102] The content of organic solvent relative to the total amount of pretreatment liquid is preferably 3% to 40% by mass, more preferably 5% to 30% by mass.

[0103] (Resin particles) The ink preferably contains at least one resin particle.

[0104] The resin constituting the resin particles is preferably a water-insoluble resin. "Water-insoluble" in water-insoluble resin refers to the property that its solubility in 100g of distilled water at 25°C is less than 2g.

[0105] 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.

[0106] In this invention, the volume average particle size refers to the value measured using a laser diffraction / scattering particle size analyzer.

[0107] As a measuring device, for example, the particle size distribution measuring device “Microtrac MT-3300II” (manufactured by Nikkiso Co., Ltd.) can be cited.

[0108] Examples of resin particles include urethane resin particles, acrylic resin particles, and ester resin particles.

[0109] Regarding resin particles, for example, see paragraphs 0038 to 0114 of International Publication No. 2021 / 192720 and paragraphs 0109 to 0120 of Japanese Patent Application Publication No. 2015-25076.

[0110] From the viewpoint of making the printed and dyed materials feel good, the ink preferably contains urethane resin particles.

[0111] When the ink contains resin particles, the content of resin particles relative to the total amount of ink is preferably 1% to 20% by mass, more preferably 2% to 15% by mass.

[0112] (additive) Regarding inks, additives such as surfactants, colloidal silica, cosensitizers, UV absorbers, antioxidants, anti-fading agents, conductive salts, and alkaline compounds may be included as needed.

[0113] (Relationship between effective cations and alkanediols) At least one of the pretreatment liquid and ink preferably contains an alkanediol, and from the viewpoint of dischargeability, both the pretreatment liquid and ink more preferably contain an alkanediol.

[0114] However, if the content of alkanediol increases, it is easy to cause bleeding. Therefore, it is preferable to maintain a balance with the effective cations in the pretreatment solution.

[0115] Specifically, when the pretreatment liquid and ink are set to have the same mass, the effective cation content in the pretreatment liquid is set to A mmol / L, and the total content of alkanediol contained in the pretreatment liquid and ink is set to B mass%, the ratio of A to B (i.e., A / B) is preferably 15 or more.

[0116] The effective cation content refers to the value obtained by dividing the content of quaternary ammonium cations (1) in 1 liter of pretreatment solution by the formula weight of each monovalent cation of quaternary ammonium cations (1).

[0117] From the viewpoint of further suppressing image bleeding, an A / B ratio of 10 or higher is more preferable. From the viewpoint of maintaining a good feel, an upper limit of 100 for A / B is preferred.

[0118] [Dyeing and Printing Methods] The printing and dyeing method of the present invention preferably includes: a pretreatment liquid application step, in which the pretreatment liquid contained in the ink kit is applied to the fabric; and an ink application step, in which the ink composition contained in the ink kit is applied to the fabric on which the pretreatment liquid has been applied.

[0119] In the printing and dyeing method of the present invention, since the ink kit of the present invention is used, it is possible to obtain printed and dyed products with excellent wash fastness, good hand feel and excellent image quality.

[0120] (Pretreatment solution application process) In the dyeing method of the present invention, firstly, a pretreatment liquid is applied to the fabric.

[0121] -Clothing- As for the types of fibers used in fabrics, examples include synthetic fibers such as nylon, polyester, and acrylonitrile; semi-synthetic fibers such as cellulose acetate and rayon; natural fibers such as cotton, silk, and wool; and mixed fibers composed of two or more types selected from the group consisting of synthetic fibers, semi-synthetic fibers, and natural fibers.

[0122] The fibers in the fabric are preferably selected from at least one of the group consisting of cotton and polyester. Examples of fabrics include woven fabrics, woven fabrics, and nonwoven fabrics. The fabric can also be a fabric for fabric products.

[0123] In particular, the fabric is in roller form and is preferably cotton or a cotton-polyester blend.

[0124] As textile products, examples include clothing (e.g., T-shirts, sweatshirts, jerseys, shorts, wetsuits, dresses, shirts, etc.), bedding, and handkerchiefs.

[0125] -Application of pretreatment solution- There are no particular limitations on the method of applying the pretreatment solution to the fabric. Examples include coating, impregnation, inkjet printing, spraying, and screen printing. However, from the viewpoint of improving the hand feel of the resulting printed fabric, the inkjet printing method is preferred. That is, it is preferable to apply the pretreatment solution using an inkjet recording method.

[0126] Inkjet recording methods can use commonly known methods, such as charge control methods that use electrostatic induction to discharge pretreatment liquid, on-demand inkjet methods (pressure pulse methods) that use the vibration pressure of piezoelectric elements, acoustic inkjet methods that convert electrical signals into sound beams and irradiate the pretreatment liquid to discharge the pretreatment liquid using radiation pressure, and thermal inkjet methods that heat the pretreatment liquid to form bubbles and utilize the resulting pressure.

[0127] Typically, image recording methods based on inkjet recording devices include shuttle scanning (also known as "serial head method"), which uses a short serial head for image recording, and single-pass method (also known as "linear head method"), which uses a linear printhead with recording elements arranged across the entire width of the recording medium. In the shuttle scanning method, image recording occurs while the serial head scans along the width of the recording medium. In contrast, in the single-pass method, the recording medium is scanned in a direction orthogonal to the arrangement direction of the recording elements, allowing image recording across the entire surface of the recording medium. Therefore, unlike the shuttle scanning method, the single-pass method does not require a transport system such as a carriage for scanning the serial head. Furthermore, the single-pass method eliminates the need for complex scanning control of the carriage movement and the recording medium; only the recording medium moves, thus increasing recording speed compared to the shuttle scanning method.

[0128] The inkjet recording method is preferably performed in a single pass. According to the printing and dyeing method of the present invention, even when printing and dyeing is performed in a single pass, it is possible to obtain printed and dyed products with excellent wash fastness, good hand feel and excellent image quality.

[0129] The ejection volume of pretreatment liquid discharged 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. Furthermore, the ejection volume refers to the volume of ink ejected from a single nozzle at one time via inkjet recording.

[0130] From a tactile perspective, the preferred application rate of the pretreatment solution is 10 g / m³. 2 ~30g / m 2 More preferably 15g / m 2 ~25g / m 2 .

[0131] The preferred resolution for discharging the pretreatment solution is 200 dpi (dots per inch) or higher × 200 dpi or higher, more preferably 400 dpi or higher × 400 dpi or higher, or 1200 dpi or lower × 1200 dpi or lower. Furthermore, "dpi" refers to the number of dots per 25.4 mm.

[0132] (Ink application process) In the printing and dyeing method of the present invention, after the pretreatment liquid application step, the ink contained in the ink kit is applied to the fabric that has been pretreated.

[0133] -Application of ink- There is no particular limitation on the method of applying ink to fabric that has been pretreated with a pretreatment solution; for example, coating, dipping, inkjet printing, spraying, and screen printing can be listed. However, from the viewpoint of improving the hand feel of the resulting printed material, inkjet printing is preferred. That is, it is preferable to apply the ink composition using an inkjet recording method. Regarding the inkjet recording method, as described in the section on pretreatment solution application,...

[0134] The 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. Furthermore, the ejection volume refers to the volume of ink ejected from a single nozzle at one time via inkjet recording.

[0135] From a tactile perspective, the preferred ink application rate is 10 g / m³. 2 ~30g / m 2 More preferably 15g / m 2 ~25g / m 2 .

[0136] The resolution in the ink discharge is preferably 200 dpi or higher × 200 dpi or higher, more preferably 400 dpi or higher × 400 dpi or higher, or 1200 dpi or lower × 1200 dpi or lower.

[0137] (Heat treatment process) The printing and dyeing method of the present invention preferably includes a step of heating the fabric with applied ink at a temperature of 100°C or higher after the ink application step.

[0138] Examples of heat treatment apparatus include heating drums, warm air, infrared lamps, heating ovens, heating plates, hot presses, and heating plates. The heating temperature is more preferably 100°C to 180°C, and even more preferably 120°C to 170°C. The heating time is preferably 5 seconds to 200 seconds, and more preferably 30 seconds to 160 seconds.

[0139] The printing and dyeing method of the present invention may include other steps besides those described above.

[0140] However, it is preferable not to include the step of washing the ink-treated fabric after the ink application process.

[0141] The printing and dyeing method of the present invention uses the above-mentioned pretreatment liquid and the above-mentioned ink. The pretreatment liquid contains an ammonium compound (1), so the pigment has excellent fixing properties on the fabric and there is no need to wash the fabric that has been inked.

[0142] Example The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments as long as it does not depart from its spirit.

[0143] [Preparation of Pretreatment Solution] The following ingredients were mixed and stirred for 60 minutes to prepare the pretreatment solution.

[0144] Quaternary ammonium salts: Quaternary ammonium salts listed in Tables 1 to 6… Contents listed in Tables 1 to 6 • Organic solvents: Organic solvents 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. ... 1.0% by mass Water… makes the pretreatment solution a total of 100% by mass. [Ink Preparation] • APD4000 Black (manufactured by Fujifilm Imaging Colorants Ltd.)...contains 4% by weight as pigment. • Organic solvents: Organic solvents 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% by mass Surfactant: Product name "BYK345", manufactured by BYK Corporation... 0.1% by mass • Polyvinylpyrrolidone: Product name "PVPK15", manufactured by Tokyo Chemical Industry Co., Ltd. ... 0.15% by mass Colloidal silica dispersion: Product name "ST-XS", manufactured by Nissan Chemical Corporation... The content of colloidal silica particles is 0.05% by mass. Water…makes the ink a 100% mass surplus. The following describes the ammonium salt and organic solvent used in the preparation of the pretreatment solution, as well as the organic solvent and resin particles used in the preparation of the ink. Furthermore, when the pretreatment solution contains quaternary ammonium cations (1), since the quaternary ammonium salt is used as a raw material, details of the raw material are shown.

[0145] In the table, ingredients that are not present are recorded as "-".

[0146] [Salts of quaternary ammonium cations (1)] • DADMAC: diallyl dimethyl ammonium chloride ·choline chloride ABDMAC: N-(2-Acryloyloxyethyl)-N-Benzyl-N,N-Dimethylammonium Chloride Compound 1: Didecyldimethylammonium chloride (product name "Dacyldimethylammonium chloride", manufactured by Sigma-Aldrich) [Catonic compounds] The following compounds are not salts of quaternary ammonium cations (1).

[0147] • PolyDADMAC: diallyl dimethyl ammonium chloride polymer (product name "PAS-H1L", manufactured by NITTOBOMEDICAL CO.,LTD.) Compound 2: Lauryltrimethylammonium chloride (product name "COTAMINE 24P", manufactured by Kao Corporation) In addition, cationic compounds are also listed in the quaternary ammonium cation column in Table 3.

[0148] [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 [Resin particles] Carbamate A: An aqueous dispersion of carbamate resin particles (product name "NeoRez R940", manufactured by Kusumoto Chemicals, Ltd.) Carbamate B: An aqueous dispersion of carbamate resin particles (product name "SUPERFLEX460", manufactured by DKSCo. Ltd.) Carbamate C: An aqueous dispersion of carbamate resin particles (product name "EVAFANOL 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 Polymer). Inkjet Printing The fabric was pretreated using the pretreatment solution prepared in the examples and comparative examples. The ink prepared in the examples and comparative examples was applied to the pretreated fabric, and heat treatment was performed to obtain the printed fabric. Details are as follows.

[0149] Prepare a long strip (15cm x 4cm) of 100% cotton fabric (product name "Cotton D5005", manufactured by Akahori Sangyo).

[0150] As an inkjet recording device, a unit equipped with an inkjet head (product name "StarFire SG-1024SA", manufactured by Fujifilm Dimatix, Inc.) and an ink circulation pump was prepared. A cloth was fixed to the worktable as the recording medium. Pretreatment liquid and ink composition were filled into the ink tank connected to the inkjet head. The inkjet head was configured in a linear arrangement, with the nozzles aligned orthogonally to the direction of movement of the worktable. Regarding the discharge conditions of the pretreatment liquid and ink, the ejection volume was set to 60 pL, the discharge frequency to 10 kHz, and the resolution to 400 dpi × 400 dpi. The ink circulation pump was activated to circulate the pretreatment liquid and ink between the ink tank and the inkjet head.

[0151] First, pretreatment liquid is discharged onto the entire surface of the recording medium, and a solid image is recorded. After drying with warm air at 60°C for 10 seconds, the ink is discharged, and the image is recorded again, thus obtaining the colored cloth.

[0152] The dyed fabric was heat-treated at 160°C for 120 seconds using a hot press (AF-54TEN type automatic flat press, manufactured by Asahi Kasei Corporation) to obtain the printed and dyed product.

[0153] <Evaluation> The above-mentioned printed and dyed materials were used to conduct the following evaluation. The evaluation methods are as follows.

[0154] (wash fastness) The dyed and printed materials were evaluated according to ISO 105-C06:2010 B1S. Furthermore, when multiple evaluation criteria were met, the highest evaluation was adopted.

[0155] AA: Both pollution and discoloration are at level 4-5.

[0156] A: Both pollution and discoloration are at level 4 or above.

[0157] B: Both pollution and discoloration are at level 3-4 or above.

[0158] C: Both pollution and discoloration are at level 3 or above.

[0159] D: Any one of pollution or discoloration is classified as Level 2.

[0160] (Image quality) Will Figure 1 The text images shown were recorded in font sizes of 10pt, 12pt, 14pt, and 16pt. The recorded text images were observed with the naked eye, and the image quality was evaluated.

[0161] AA: No text image distortion in all font sizes of 10pt, 12pt, 14pt and 16pt.

[0162] A: There was no distortion of the text image in the 12pt, 14pt and 16pt font sizes, but distortion was observed in the 10pt font size.

[0163] B: No text image distortion was observed in 14pt and 16pt font sizes, but distortion was observed in 10pt and 12pt font sizes.

[0164] C: No text image distortion was observed at the 18pt font size, but distortion was observed at the 10pt, 12pt, and 14pt font sizes.

[0165] D: Deformation of the text image was observed in all font sizes of 10pt, 12pt, 14pt and 16pt.

[0166] (Feel) A rectangular evaluation sample with a length (long side) of 150 mm and a width (short side) of 50 mm was cut from the obtained printed fabric. 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 the evaluation fixture. The evaluation fixture was erected with the short side vertical and the long side horizontal. Next, the center of the evaluation sample along its length (i.e., the centerline) was placed on the long side of the horizontally oriented evaluation fixture, with both sides (end sides) of the evaluation sample hanging down.

[0167] In this state, the straight-line distance between one end and the other end of the length direction of the evaluation sample was measured, and the hand feel of the printed and dyed material was evaluated according to the following evaluation criteria. In this evaluation, the softer the evaluation sample (i.e., the better the hand feel), the more the two sides of the evaluation sample sag due to their own weight (i.e., the evaluation sample bends), and as a result, the straight-line distance between one end and the other end of the length direction of the evaluation sample becomes shorter.

[0168] AA: Straight-line distance less than 40mm.

[0169] A: The straight-line distance is more than 40mm and less than 55mm.

[0170] B: The straight-line distance is more than 55mm and less than 70mm.

[0171] C: The straight-line distance is 70mm or more and less than 85mm.

[0172] D: Straight-line distance is 85mm or more.

[0173] (Abrasion resistance) The dyed and printed fabrics were evaluated according to ISO 105X12:2001 (wet). A: Level 3-4 and above B: Level 3 C: Level 2-3 D: Level 2 and below The evaluation results are shown in Tables 1 to 6.

[0174] In Table 6, compound 2 does not belong to the quaternary ammonium cation (1), but it is recorded that R is equivalent to that in formula (1). 1 and R 2 . group.

[0175] [Table 1]

[0176] [Table 2]

[0177] [Table 3]

[0178] [Table 4]

[0179] [Table 5]

[0180] [Table 6]

[0181] As shown in Tables 1 to 6, in Examples 1 to 23, the quaternary ammonium cation (1) with a formula amount of 100 to 300 is included. The content of the quaternary ammonium cation represented by formula (1) is 5% to 30% by mass relative to the total amount of the pretreatment liquid. Therefore, it is possible to obtain printed and dyed products with excellent washing fastness, good hand feel and excellent picture quality.

[0182] It can be seen that Comparative Example 1 does not contain quaternary ammonium cations (1) and has a poor feel.

[0183] It can be seen that in Comparative Example 2, the content of quaternary ammonium cation (1) exceeded 300 and the texture was poor.

[0184] It can be seen that in Comparative Example 3, the quaternary ammonium cation contains groups with more than 10 carbon atoms and has poor image quality.

[0185] It can be seen that in Comparative Example 4, the content of quaternary ammonium cation (1) is less than 5% by mass and the image quality and feel are poor.

[0186] It can be seen that in Comparative Example 5, the content of quaternary ammonium cation (1) exceeded 30% by mass and the texture was poor.

[0187] It can be seen that in Example 4, the content of alkanediol in the pretreatment solution is more than 3% by mass, and the abrasion resistance is excellent compared with Example 8.

[0188] It can be seen that in Example 3, the content of alkanediol in the pretreatment solution is less than 30% by mass, and compared with Example 9, the image quality, feel and scratch resistance are excellent.

[0189] It can be seen that in Example 21, the content of alkylene glycol alkyl ether in the ink is more than 2% by mass, and the abrasion resistance is excellent compared with Example 22.

[0190] It can be seen that in Example 13, the content of alkylene glycol alkyl ethers in the ink is less than 20% by mass, and the image quality and feel are superior compared with Example 23.

[0191] It can be seen that in Examples 1, 11 and 12, the ink contains urethane resin particles, and has a superior feel compared to Example 10.

[0192] Furthermore, the entire disclosure of Japanese Patent Application No. 2023-168522, filed on September 28, 2023, is incorporated herein by reference. Moreover, all documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as the specific documents, patent applications, and technical standards specifically described and incorporated herein by reference.

Claims

1. A pretreatment solution for printing and dyeing, comprising 100 to 300 of the following quaternary ammonium cation represented by formula (1), wherein, The content of the quaternary ammonium cation represented by formula (1) is 5% to 30% by mass relative to the total amount of the pretreatment solution for dyeing and printing. The pretreatment solution for printing and dyeing is used before recording images on the fabric using printing and dyeing inks containing pigments. In equation (1), R 1 and R 2 All of them are groups with fewer than 10 carbon atoms.

2. The pretreatment solution for printing and dyeing according to claim 1, wherein, The R 1 and R 2 It is a group having 10 or fewer carbon atoms and is independently an unsubstituted alkyl, substituted alkyl, vinyl, aryl, allyl, alkyl ester, (meth)acryloyl or amino group.

3. The pretreatment solution for printing and dyeing according to claim 1, wherein, It also contains alkanediols. The content of the alkanediol is 3% to 30% by mass relative to the total amount of the pretreatment solution for printing and dyeing.

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

5. The pretreatment solution for printing and dyeing according to claim 1, wherein, The formula weight of the quaternary ammonium cation represented by formula (1) is 100 to 200.

6. A printing and dyeing ink kit, comprising: The pretreatment solution for printing and dyeing according to any one of claims 1 to 5; and Printing inks containing pigments.

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

8. The ink kit for printing and dyeing according to claim 6, wherein, At least one of the pretreatment solution for printing and dyeing and the ink for printing and dyeing contains alkanediol. When the pretreatment solution and the ink for printing and dyeing are of the same mass, the effective cation content in the pretreatment solution is set to A mmol / L, and the total content of alkanediol contained in the pretreatment solution and the ink for printing and dyeing is set to B% by mass, the following conditions apply. The ratio of A to B is 15 or more.

9. The ink kit for printing and dyeing according to claim 6, wherein, The printing and dyeing ink also contains alkylene glycol alkyl ethers. The content of the alkylene glycol alkyl ether is 2% to 20% by mass relative to the total amount of the printing and dyeing ink.

10. The ink kit for printing and dyeing according to claim 6, wherein, The printing and dyeing ink also contains urethane resin particles.

11. The ink kit for printing and dyeing according to claim 6, wherein, The pigment is dispersed in a polymer containing a cross-linked structure.

12. A dyeing and printing method, comprising: The pretreatment liquid application step involves applying the pretreatment liquid for printing and dyeing contained in the ink kit for printing and dyeing as described in claim 6 to the fabric. and The ink application process involves applying the inks included in the ink kit for printing and dyeing as described in claim 6 to a fabric that has already been treated with the pretreatment liquid for printing and dyeing.

13. The dyeing and printing method according to claim 12, wherein, In the pretreatment liquid application process, the pretreatment liquid for printing and dyeing is applied by inkjet recording.

14. The dyeing and printing method according to claim 13, wherein, The inkjet recording method is performed in a single pass.

15. The dyeing and printing method according to claim 12, wherein, include: The process of heating the fabric to which the printing ink has been applied after the ink application process at a temperature of 100°C or higher.

16. The dyeing and printing method according to claim 12, wherein, Not included: The step after the ink application process is to wash the fabric to which the printing ink has been applied.

17. The dyeing and printing method according to claim 12, wherein, The fabric is roll-shaped and is made of cotton or a cotton-polyester blend.

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