JP2024048939A - Pretreatment agent for ink-jet printing and ink-jet printing method - Google Patents

Abstract

[Problem] To provide a pretreatment agent for inkjet textile printing that allows inkjet printing without drying the pretreated fabric, has the viscosity required for a screen textile printing machine, prevents color bleeding in the resulting printed fabric, and provides good texture and color. [Solution] A pretreatment agent for inkjet textile printing that contains an N-vinylformamide cationic polymer and a paste, the paste containing a cellulose derivative. An inkjet textile printing method that includes pretreating a fabric with this pretreatment agent for inkjet textile printing, and inkjet printing the pretreated area of the pretreated fabric without drying the pretreated fabric. [Selected Figure] None

Description

The present invention relates to a pretreatment agent for inkjet textile printing and an inkjet textile printing method.

Compared to conventional methods that use plates, inkjet printing has the advantage that it does not require cleaning or storage of plates, can be easily applied to a wide variety of products, and can shorten delivery times. However, inkjet printing requires expensive equipment and ink, and a pretreatment process. Patent documents 1 to 3 disclose techniques in which a pretreatment agent is applied to fabric and then dried, followed by inkjet printing. Patent documents 4 and 5 disclose techniques in which a pretreatment agent is applied to fabric and then inkjet printed without drying.

Japanese Patent Application Laid-Open No. 11-302987 JP 2003-3385 A Japanese Patent Application Laid-Open No. 9-279487 JP 2017-530269 A JP 2016-089288 A

The methods of drying the pretreatment agent after application as described in Patent Documents 1 to 3 require space for installing a dryer, and the energy and cost required for drying, and have lower productivity than methods that do not involve drying. For this reason, there is a demand for inkjet printing (textile printing) that can be performed without drying after application of the pretreatment agent.
However, methods in which the pretreatment agent is not dried after application, such as those described in Patent Documents 4 and 5, have problems in that the ink tends to bleed due to capillary action and the ink is poorly penetrable into the interior of the fabric.

As a result of the inventor's investigations, it was found that the use of a specific cationic polymer in a pretreatment agent makes it possible to print without drying and prevents color bleeding. However, it was also found that the use of a cationic polymer in a pretreatment agent does not provide the viscosity required for printing with a screen printing machine, and that the use of a glue to increase the viscosity can result in color bleeding, poor texture, and a poor color tone of the fabric after printing, depending on the type of glue.

The present invention aims to provide a pretreatment agent for inkjet textile printing that contains a cationic polymer and a sizing agent, and that enables inkjet printing without drying after application of the pretreatment agent, thereby improving productivity, reducing costs, saving energy, and saving space, and that prevents color bleeding in the resulting printed textile, resulting in good texture and color, and an inkjet textile printing method.

The inventors discovered that by applying a pretreatment agent for inkjet printing, which combines a specific cationic polymer and a specific sizing agent, to fabric, it is possible to perform inkjet printing without drying the pretreated fabric, thereby obtaining the viscosity required for screen printing machines and resolving problems with bleeding, texture, and color.

The present invention has the following aspects:

[1] A pretreatment agent for ink-jet textile printing, comprising an N-vinylformamide cationic polymer and a sizing agent, the sizing agent containing a cellulose derivative.
[2] The pretreatment agent for ink-jet textile printing according to [1], wherein the cellulose derivative is methyl cellulose.
[3] The pretreatment agent for ink-jet textile printing according to [1] or [2], wherein a content ratio (mass ratio) of the paste to the N-vinylformamide cationic polymer is 1.0 or more and 15.0 or less.
[4] The pretreatment agent for inkjet textile printing according to any one of [1] to [3], wherein a content of the N-vinylformamide cationic polymer in the total mass of the pretreatment agent for inkjet textile printing (100 mass %) is 0.1 mass % or more and 5.0 mass % or less.
[5] The pretreatment agent for ink-jet textile printing according to any one of [1] to [4], wherein a content of the cellulose derivative in the total mass of the pretreatment agent for ink-jet textile printing (100 mass %) is 0.5 mass % or more and 5.0 mass % or less.
[6] The pretreatment agent for ink-jet textile printing according to any one of [1] to [5], comprising the cellulose derivative as a first sizing agent and further comprising an inorganic compound as a second sizing agent.
[7] The pretreatment agent for ink-jet textile printing according to [6], wherein the inorganic compound is montmorillonite.
[8] The pretreatment agent for ink-jet textile printing according to any one of [1] to [7], further comprising a defoaming agent.
[9] The pretreatment agent for ink-jet textile printing according to any one of [1] to [8], wherein the N-vinylformamide cationic polymer contains at least one selected from the group consisting of polyamidines and polyvinylamines.
[10] An inkjet textile printing method comprising pretreating a fabric with the pretreatment agent for inkjet textile printing according to any one of [1] to [9], and inkjet printing on the pretreated area of the pretreated fabric without drying the pretreated fabric.
[11] The ink-jet textile printing method according to [10], wherein the ink used for the ink-jet printing is a disperse dye.

The inkjet textile printing pretreatment agent and inkjet textile printing method of the present invention allow inkjet printing of fabrics without drying the fabric that has been pretreated after application of the pretreatment agent, and also ensures the viscosity required for printing with a screen printing machine, while preventing color bleeding and allowing the production of printed fabrics with good texture and color.

The inkjet textile printing pretreatment agent (hereinafter, simply referred to as the "pretreatment agent") of the present invention will be described in detail below. The following explanation of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

[Pretreatment agent]
The pretreatment agent of the present invention contains an N-vinylformamide cationic polymer and a specific sizing agent. The pretreatment agent of the present invention may further contain a defoaming agent or a deep-dyeing agent, for example, a deep-dyeing agent that is compatible with the N-vinylformamide cationic polymer. The pretreatment agent of the present invention may contain optional components such as water and an organic solvent.

<Flocculant>
The pretreatment agent of the present invention contains an N-vinylformamide cationic polymer. The N-vinylformamide cationic polymer acts as a flocculant, that is, has the function of flocculating dyes.

The pretreatment agent of the present invention may contain a flocculant other than the N-vinylformamide cationic polymer. In this case, the flocculant is not particularly limited as long as it has the effect of flocculating the dye, but examples of the flocculant include organic acids, polyvalent metal salts, cationic low molecular weight compounds, and cationic polymers other than the N-vinylformamide cationic polymer.

The organic acids include formic acid, acetic acid, propionic acid, butyric acid, tartaric acid, citric acid, and lactic acid.
As the polyvalent metal salt, a compound composed of a divalent or higher metal ion and an anion can be used. Examples of the divalent or higher metal ion include calcium, magnesium, aluminum, titanium, strontium, iron, etc. Examples of the anion include chloride ion, bromide ion, nitrate ion, sulfate ion, carbonate ion, hydroxide ion, etc.
Examples of cationic low molecular weight compounds include (2-hydroxyethyl)trimethylammonium chloride, benzoylcholine chloride, benzyltriethylammonium chloride, trimethylacetohydrazide ammonium chloride, 1-butyl-1-methylpyrrolidinium chloride, 3-hydroxy-4-(trimethylammonio)butyrate hydrochloride, glycidyltrimethylammonium chloride, and L-carnitine hydrochloride.
Examples of cationic polymers other than N-vinylformamide-based cationic polymers include polydiallyldimethylammonium chloride, polyallylamine or its derivatives, amine-epihalohydrin copolymers, and other quaternary ammonium salt-type cationic polymers.

(N-vinylformamide cationic polymer)
The pretreatment agent of the present invention contains an N-vinylformamide cationic polymer. The N-vinylformamide cationic polymer is a cationic polymer obtained by polymerization using N-vinylformamide, and has the effect of enhancing the adhesion of the ink to the fabric. The effect of enhancing the adhesion of the ink is related to the level of cationicity.

The N-vinylformamide cationic polymer is not particularly limited, and examples thereof include polyamidine and polyvinylamine. The polyamidine can be obtained by copolymerization of acrylonitrile and N-vinylformamide. Only one type of N-vinylformamide cationic polymer may be used, or two or more types may be used in combination. The N-vinylformamide cationic polymer preferably contains one or more types selected from the group consisting of polyamidine and polyvinylamine.

As the N-vinylformamide cationic polymer, commercially available products may be used. Examples of polyamidines include PVADL (manufactured by Mitsubishi Chemical Corporation), SC-700, and SC-700L (all manufactured by Hymo Corporation). Examples of polyvinylamines include PVAM0570B, PVAM0595B, and KP8040 (all manufactured by Mitsubishi Chemical Corporation).

<Sizing agent>
The pretreatment agent of the present invention contains a sizing agent. By blending the sizing agent, the viscosity of the pretreatment agent can be adjusted to an appropriate level.
In the present invention, the paste contains at least a cellulose derivative. The cellulose derivative is nonionic, and the nonionic paste is less likely to cause a complex with the N-vinylformamide polymer than an anionic paste, so that the texture of the printed matter can be improved.
Tamarind gum is also a nonionic compound that can be used as a sizing agent, but it contains carboxylic acid components such as citric acid and succinic acid, which act as anions, and are therefore thought to deteriorate the texture of the resulting printed material.

Examples of cellulose derivatives include hydroxyethyl cellulose, methyl cellulose, and hydroxypropyl methyl cellulose. These cellulose derivatives may be used alone or in combination of two or more. Of these, hydroxyethyl cellulose and methyl cellulose are preferred, with methyl cellulose being more preferred, since they provide a stable and appropriate viscosity when mixed with an N-vinylformamide cationic polymer.

The pretreatment agent of the present invention may contain a cellulose derivative as a first sizing agent and an inorganic compound as a second sizing agent. By using a cellulose derivative in combination with an inorganic compound, it is possible to improve the cleanability when washing off unfixed dyes and auxiliaries from the fabric.
Examples of the inorganic compound as the second sizing agent include montmorillonite, silica, etc. These may be used alone or in combination of two or more kinds.
Among these, montmorillonite is preferred because it is unlikely to cause a complex with the N-vinylformamide polymer even if the amount added is increased.

Examples of commercially available cellulose derivatives include methylcellulose (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) and hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of commercially available inorganic compounds include montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) and montmorillonite (Sumecton, manufactured by Kunimine Kogyo Co., Ltd.).

<Antifoaming agent>
The pretreatment agent of the present invention may contain an antifoaming agent. By incorporating an antifoaming agent, color bleeding can be more reliably prevented and the texture can be improved.
As the defoaming agent, any of those used in normal fiber treatment can be used, for example, alcohol-based defoaming agents, fatty acid derivative-based defoaming agents, and silicone-based defoaming agents can be mentioned. Among them, from the viewpoint of cleaning properties when washing off dyes and auxiliaries not fixed to the fabric, it is preferable to include one or more selected from the group consisting of alcohol-based defoaming agents and fatty acid derivative-based defoaming agents, and it is more preferable to include an alcohol-based defoaming agent. As the defoaming agent, only one type may be used, or two or more types may be used in combination.

(Alcohol-based defoamer)
The alcohol-based defoaming agent preferably has an HLB value of 15 or less, and more preferably 10 or less.
As the alcohol-based defoaming agent, a higher alcohol can be preferably used. The number of carbon atoms of the higher alcohol is preferably 12 or more, and is preferably 25 or less, and more preferably 22 or less. For example, 12 to 25 is preferable, and 12 to 22 is more preferable.
The alcohol-based defoaming agent may be any of primary alcohols, secondary alcohols, and tertiary alcohols, with primary alcohols and secondary alcohols being preferred.
Furthermore, as the alcohol-based defoaming agent, either a monohydric alcohol or a polyhydric alcohol can be used. The number of hydroxyl groups in the alcohol is preferably 2 or more, and is preferably 4 or less, and more preferably 3 or less. For example, 2 to 4 is preferred, and 2 to 3 is more preferred.
As the alcohol-based defoaming agent, an alcohol having an ether group can also be preferably used. Examples of the alcohol having an ether group include polyalkylene glycol-based compounds and compounds obtained by addition polymerization of an alkylene oxide with a higher alcohol. In this case, ethylene oxide or propylene oxide can be used as the alkylene oxide. Among them, polyalkylene glycol-based compounds are preferred, and among them, polyethylene glycol-based compounds are more preferred. Moreover, it is more preferred that the polyethylene glycol-based compound has an alkyl group. That is, an alkyl-polyethylene glycol-based compound is more preferred.
In addition to the above, examples of the alcohol-based defoaming agent include diamylphenoxyethanol, 3-heptanol, 2-ethylhexanol, acetylene alcohol, acetylene glycol, isopropyl alcohol, and alkyl-polyethylene glycol compounds.
Among the above, higher alcohols and alcohols having an ether group are preferred, higher alcohols and polyalkylene glycol compounds are more preferred, higher alcohols and polyethylene glycol compounds are even more preferred, and higher alcohols and alkyl-polyethylene glycol compounds are particularly preferred.
Commercially available alcohol-based defoamers include, for example, Antifloss F-102 and F-103 (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and Defoamer (manufactured by Furukawa Chemical Industries Co., Ltd.).

(Fatty acid derivative defoamer)
The fatty acid derivative-based defoaming agent preferably has an HLB value of 15 or less, and more preferably 10 or less.
Examples of fatty acid derivative-based defoamers include mineral oil, sorbitan fatty acid ester, fatty acid ester, glycerin fatty acid ester, and sucrose fatty acid ester. Among these, mineral oil is preferred because of its immediate effect. As the mineral oil, long-chain alkyl-based ones are preferred.
The number of carbon atoms of the fatty acid used as the raw material of the fatty acid derivative of the fatty acid derivative-based defoaming agent is preferably 16 or more, more preferably 18 or more. On the other hand, it is preferably 24 or less, more preferably 22 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 16 or more and 24 or less, more preferably 18 or more and 22 or less.
Examples of fatty acids used as raw materials for fatty acid derivatives of fatty acid derivative-based defoamers include stearic acid, oleic acid, erucic acid, and behenic acid. Among these, stearic acid is preferred.
Commercially available fatty acid derivative-based defoaming agents include, for example, S-39H and S-49H (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and NK-2 (manufactured by Osaka Chemical Co., Ltd.).

(Silicone-based defoaming agent)
Silicone-based defoaming agent is not particularly limited. For example, it can be either water-based or non-water-based, and it can be oil-based, which is composed of silicone oil, oil compound-based, which is made by adding dispersant to silicone oil, emulsion-based, which is made by emulsionizing silicone oil, or self-emulsifying-based. Among them, emulsion-based is preferred from the viewpoint of supplementing dispersibility in water. Among the emulsion-based, O/W-based is more preferred.
Specific examples of silicone-based defoaming agents include polydimethylsiloxane, dimethylsilicone, and fluorosilicone. Among these, polydimethylsiloxane is preferred.
Examples of commercially available silicone-based defoamers include TSA730, TSA732, TSA770, TSA772, TSA7341, YMA6509, TSA780 (all manufactured by GE Toshiba Silicones), M-6500, M-700 (all manufactured by Ichiho), Antifoam SS, Antifoam S-8 (all manufactured by Nissei Chemical Industry Co., Ltd.), KM-70, KM-71, KM-73, KM-73A, KM-90, KM-89, KM-83A, KM-75, KS-502, KS-537, KM-98, KM-7750, and X-50-1041 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

<Dyeing agent>
The pretreatment agent of the present invention may contain a deep-dyeing agent. The incorporation of the deep-dyeing agent can further improve the permeability of the ink into the fabric.
The deep-dyeing agent is preferably one compatible with the N-vinylformamide cationic polymer among deep-dyeing agents used in normal fiber treatment. The phrase "the deep-dyeing agent is compatible with the N-vinylformamide cationic polymer" means that when 250 g each of a 1% by mass N-vinylformamide cationic polymer aqueous solution and a 1% by mass deep-dyeing agent aqueous solution are mixed, left at 25° C. for 24 hours, and then filtered through an 80 mesh sieve, the sieve residue is less than 10 g.

The dyeing agent compatible with the N-vinylformamide cationic polymer is not particularly limited, and examples thereof include amides, glycol ethers, and polyethers. Among these, amides are preferred, and among these, N-alkylol amides are more preferred. As the dyeing agent, only one type may be used, or two or more types may be used in combination.

Commercially available dye deepening agents include, for example, Sanflorene SN (N-alkylolamide, manufactured by Nicca Chemical Co., Ltd.), Hiol 420 (glycol ether of higher alcohol, manufactured by Hayashi Chemical Co., Ltd.), and Cellopol PA-19S (manufactured by Sanyo Chemical Co., Ltd.).

<Optional ingredients>
The pretreatment agent of the present invention may contain optional components such as water, organic solvents, polyvalent metal salts, organic acids, dissolution aids, viscosity adjusters, pH adjusters, reduction inhibitors, preservatives, and surfactants, provided that the effects are not impaired. The organic solvent is not particularly limited, and examples thereof include glycerin, ethylene glycol, diethylene glycol, 1,2-hexanediol, and propylene glycol.

<Composition>
The composition of the pretreatment agent of the present invention will be described below.
In the following description of the composition, "content" means "the proportion of the active ingredient contained in that agent in the pretreatment agent", and "mixing rate" means "the proportion of the blended amount (added amount) of the agent itself, that is, including not only the active ingredient but also a solvent such as water, if present, in the pretreatment agent".

The content of the N-vinylformamide cationic polymer in the pretreatment agent of the present invention varies depending on the type of fabric to be treated, the amount of the pretreatment agent applied, etc., but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, as the solid content relative to 100% by mass of the total mass of the pretreatment agent. If the content of the N-vinylformamide cationic polymer is equal to or more than the lower limit, the adhesion of the ink to the fabric is easily improved. The upper limit of the content of the N-vinylformamide cationic polymer is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, as the solid content relative to 100% by mass of the total mass of the pretreatment agent. If the content of the N-vinylformamide cationic polymer is equal to or less than the upper limit, the cleanability when washing off the dye and auxiliary agent not fixed to the fabric is improved, and the texture is also improved.
The upper and lower limits can be arbitrarily combined. For example, the content is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.2% by mass or more and 3.0% by mass or less.

The content of the cellulose derivative in the pretreatment agent of the present invention varies depending on the viscosity required for the application method of the pretreatment agent, but from the viewpoint of facilitating the increase in the viscosity of the pretreatment agent, the solid content relative to 100% by mass of the total mass of the pretreatment agent is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 0.8% by mass or more. On the other hand, from the viewpoint of excellent detergency when washing off dye and auxiliary agents not fixed to the fabric, the content of the cellulose derivative is preferably 5.0% by mass or less, more preferably 4.5% by mass or less, and even more preferably 4.0% by mass or less, in terms of the solid content relative to 100% by mass of the total mass of the pretreatment agent.
The upper and lower limits can be arbitrarily combined. For example, the content is preferably 0.5% by mass or more and 5.0% by mass or less, more preferably 0.7% by mass or more and 4.5% by mass or less, and even more preferably 0.8% by mass or more and 4.0% by mass or less.

When the pretreatment agent of the present invention contains a cellulose derivative and another paste as a paste, the total paste content in the pretreatment agent of the present invention varies depending on the viscosity required for the application method of the pretreatment agent, but in order to facilitate increasing the viscosity of the pretreatment agent, the solid content is preferably 1.0% by mass or more, and more preferably 1.5% by mass or more, relative to 100% by mass of the total mass of the pretreatment agent. On the other hand, in order to provide excellent cleanability when washing off dyes and auxiliaries that have not been fixed to the fabric, the paste content is preferably 5.0% by mass or less, and more preferably 4.5% by mass or less, relative to 100% by mass of the total mass of the pretreatment agent.
The upper and lower limits can be arbitrarily combined. For example, the content is preferably 1.0% by mass or more and 5.0% by mass or less, and more preferably 1.5% by mass or more and 4.5% by mass or less.

When the pretreatment agent of the present invention contains a cellulose derivative and an inorganic compound such as montmorillonite as a sizing agent, from the viewpoint of obtaining a good balance between the viscosity improving effect due to the inclusion of the cellulose derivative and the cleanability effect due to the inclusion of the inorganic compound when washing off unfixed dyes and auxiliary agents from the fabric, the content of the cellulose derivative in the total of 100% by mass of the cellulose derivative and the inorganic compound is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 80% by mass or less.

From the viewpoint of effectively obtaining the blending effect of the sizing agent, the content ratio (mass ratio) of the sizing agent to the N-vinylformamide cationic polymer in the pretreatment agent of the present invention is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 2.0 or more. On the other hand, from the viewpoint of texture, the upper limit of the content ratio is preferably 15.0 or less, more preferably 12.0 or less, even more preferably 10.0 or less, and particularly preferably 6.0 or less.
The upper and lower limits can be combined in any combination. For example, the range is preferably 1.0 to 15.0, more preferably 1.2 to 12.0, even more preferably 2.0 to 10.0, and particularly preferably 2.0 to 6.0.

When the pretreatment agent of the present invention contains an antifoaming agent, the blending ratio of the antifoaming agent in the pretreatment agent is preferably 0.02% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2.0% by mass or more, relative to 100% by mass of the total mass of the pretreatment agent, from the viewpoints of texture and cleanability, while the blending ratio of the antifoaming agent is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, relative to 100% by mass of the total mass of the pretreatment agent, from the viewpoints of bleeding prevention.
The upper and lower limits can be arbitrarily combined. For example, the content is preferably 0.02% by mass or more and 5.0% by mass or less, more preferably 1.5% by mass or more and 4.0% by mass or less, and even more preferably 2.0% by mass or more and 4.0% by mass or less.

When the pretreatment agent of the present invention contains a deep-dyeing agent, the blending ratio of the deep-dyeing agent in the pretreatment agent is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, and even more preferably 4.0% by mass or more, relative to the total mass 100% of the pretreatment agent, from the viewpoint of excellent ink penetration into the fabric. On the other hand, the blending ratio of the deep-dyeing agent is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, even more preferably 10.0% by mass or less, and particularly preferably 8.0% by mass or less, relative to the total mass 100% of the pretreatment agent, from the viewpoint of preventing the ink from bleeding.
The upper and lower limits can be arbitrarily combined. For example, the content is preferably 1.0% by mass or more and 20.0% by mass or less, more preferably 3.0% by mass or more and 15.0% by mass or less, even more preferably 4.0% by mass or more and 10.0% by mass or less, and particularly preferably 4.0% by mass or more and 8.0% by mass or less.

When the pretreatment agent of the present invention contains a deep-dyeing agent, the amount of the deep-dyeing agent in the pretreatment agent is preferably 400 parts by mass or more, and more preferably 450 parts by mass or more, relative to 100 parts by mass of the total mass of the N-vinylformamide polymer, from the viewpoint of excellent ink penetration into the fabric. The upper limit of the amount of the deep-dyeing agent is preferably 2000 parts by mass or less, and more preferably 1500 parts by mass or less, relative to the total mass of the N-vinylformamide polymer, from the viewpoint of preventing the ink from bleeding.
The upper and lower limits can be combined in any combination. For example, the amount is preferably 400 parts by mass or more and 2000 parts by mass or less, and more preferably 450 parts by mass or more and 1500 parts by mass or less.

The amount of the dye-deepening agent in the pretreatment agent of the present invention is preferably 200 parts by mass or more, and more preferably 300 parts by mass or more, per 100 parts by mass of the total mass of the paste, from the viewpoint of the penetration of the dye during the color development process. On the other hand, from the viewpoint of bleeding, the upper limit of the amount of the dye-deepening agent is preferably 2500 parts by mass or less, and more preferably 2000 parts by mass or less, per 100 parts by mass of the total mass of the paste.

[Method of manufacturing the pretreatment agent]
The method for producing the inkjet printing pretreatment agent of the present invention is not particularly limited, but may be a method in which an N-vinylformamide cationic polymer and a paste are mixed and stirred. A known stirrer can be used for stirring.

[Inkjet printing method]
The inkjet printing method of the present invention includes the steps of pretreating a fabric with the inkjet printing pretreatment agent of the present invention, and inkjet printing the pretreated area of the fabric without drying the pretreated fabric.

<Pretreatment agent application process>
The material of the fabric to be pretreated is not particularly limited as long as it is a fabric that is usually used in ink-jet printing, and an example of the material is polyester.
The pretreatment of the fabric can be carried out, for example, by applying the pretreatment agent of the present invention to the fabric. Examples of the method for applying the pretreatment agent of the present invention include a method for immersing the fabric in the pretreatment agent, a method for applying the pretreatment agent with a roll coater, a method for applying the pretreatment agent with a squeegee, and a method for spraying the pretreatment agent with a spray device. The method for applying the pretreatment agent with a squeegee is more preferable because it can be applied only to the area to which the inkjet ink is to be applied and can be operated with a simple device.

<Inkjet printing process>
In the inkjet printing method of the present invention, inkjet printing is performed on a fabric pretreated with the pretreatment agent of the present invention without drying it. However, "inkjet printing is performed on a pretreated fabric without drying it" means that inkjet printing is performed on the area to which the pretreatment agent has been applied while the pretreatment agent on the fabric is in a liquid state.
An example of the ink used in ink-jet printing is a disperse dye. The pretreatment agent of the present invention is particularly suitable for use in ink-jet printing of polyester fabrics using a disperse dye.

The inkjet printing method of the present invention can employ known methods, except that the inkjet printing is performed using the inkjet printing pretreatment agent of the present invention and the pretreated fabric is not dried. For example, after inkjet printing, the ink is penetrated into the interior of the fabric by dry heat treatment (oven) or vapor heat treatment (steaming), and unfixed dye and auxiliary agents are washed off from the fabric by a cleaning treatment. Known cleaning methods can be employed as the cleaning treatment, but reduction cleaning is preferred, and alkaline reduction treatment is more preferred.

As explained above, the present invention uses the pretreatment agent of the present invention, which contains an N-vinylformamide cationic polymer and a paste containing at least a cellulose derivative. By using the pretreatment agent of the present invention, the viscosity required for printing with a screen printing machine can be obtained, and even if the pretreatment agent is applied and then inkjet printed without drying, color bleeding can be prevented and a printed product with excellent texture and color can be obtained. Furthermore, by not drying the pretreatment agent after application, productivity can be improved and costs, energy savings, and space savings can be achieved.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following description.

[material]
The materials used in the examples and comparative examples are shown below.
<N-vinylformamide-based cationic polymer>
PVADL: Polyamidine (product name "PVADL", manufactured by Mitsubishi Chemical Corporation, aqueous solution with polymer concentration of 26%)
<Sizing agent>
Methylcellulose (product name: Marporose M4000, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.)
Hydroxyethyl cellulose (product name: SANHEC
M", manufactured by Sanshosha)
Polyvinyl alcohol (product name: Denka Poval K-17E, manufactured by Denka Company Ltd.)
Modified guar gum (product name: Maypro Gum NP, manufactured by Sansho Co., Ltd.)
Starch (product name "Solvitose C5", manufactured by Avebe)
Tamarind gum Montmorillonite 1 (product name "Kunipia F", manufactured by Kunimine Kogyo Co., Ltd.)
Montmorillonite 2 (product name "Sumecton", manufactured by Kunimine Kogyo Co., Ltd.)
<Antifoaming agent>
Alcohol-based (product name: "Antifoaming agent", Furukawa Chemical Industry Co., Ltd., contains higher alcohol)

[Examples 1 to 9 and Comparative Examples 1 to 6]
<Preparation of pretreatment agent>
A pretreatment agent was prepared according to the composition shown in Table 1. Specifically, each component was placed in a container and stirred for 2 hours using a stirrer, and then left to stand overnight for aging.
The units of the values expressing the content or blending ratio of each component in Table 1 are mass%, and the N-vinylformamide cationic polymer and the paste are expressed as the content of the active ingredient (solid content) relative to 100 mass% of the total mass of the pretreatment agent. The blending ratio of the defoamer is the blending ratio relative to 100 mass% of the total mass of the pretreatment agent. In addition, in order to enable application by a screen printing machine in the pretreatment step described below, the content of the paste was adjusted so that the liquid viscosity of the pretreatment agent was 2000 mPa·s or more. Water was added after adjusting so that the total amount of the pretreatment agent was 100 mass%. Note that a column without a numerical value in Table 1 means that the component was not contained.

<Pretreatment>
Using a screen printing machine (Tsujii Senki Kogyo Co., Ltd. SP300ARD), the fabric attached to a polyvinyl chloride plate using an adhesive was placed under a 120-mesh screen, the pretreatment agent was pooled in the area above the screen where there was no fabric, and the metal roll was moved with an electromagnet to apply the pretreatment agent evenly to the fabric. The amount of pretreatment agent applied was 1.0 to 1.5 g/ ^cm2 , although it was affected by the viscosity of the pretreatment agent composition, the electromagnetic force, and the basis weight of the fabric.

<Inkjet printing>
For the fabrics of Examples 1 to 9 and Comparative Examples 1 to 6, within 5 seconds after application of the pretreatment agent, i.e., before the applied pretreatment agent had dried, the fabric was transferred to an inkjet device (Inkjet Lab, manufactured by Cluster Technology Co., Ltd.), and ink was applied to the areas where the pretreatment agent had been applied.
The ink used was black dispersion ink manufactured by Toshin Kogyo Co., Ltd. The fabric used was polyester crepe de chine (density: warp 221 threads/inch, weft 108 threads/inch, basis weight 91 g/m ² ) manufactured by Shikisen Co., Ltd.
The printed image pattern used was a grid pattern, with the grid size being 2 mm square and the line thickness being 0.2 mm.

<Steam heat treatment>
The ink-coated fabric was subjected to a steaming treatment at 170° C. for 10 minutes using a Tsujii Senki Kogyo Co., Ltd. HT-3-550 HT steamer.

<Cleaning treatment>
The fabric after the steaming treatment was washed with water for 10 minutes by rubbing it twice per second. After dissolving 2 g/L of surfactant (Amylazine D), 2 g/L of sodium hydrosulfite, and 2 g/L of NaOH (granules) in 80°C warm water, the washed fabric was added and reduced for 10 minutes to wash away the pretreatment agent and excess ink adhering to the fabric. After reduction washing, the fabric was washed with water again to wash away the reduction cleaning agent adhering to the fabric.

[Reference Example 1]
In Reference Example 1, a pretreatment agent not containing a cationic polymer was prepared, and after application of the pretreatment agent, it was dried for 10 minutes with a dryer before inkjet printing. The composition of the pretreatment agent in Reference Example 1 is shown below.
<Glue> Sodium alginate powder (manufactured by Tanaka Direct Dye Store): 4.2% by mass
<Dye deepening agent> N-alkylolamide (product name "Sunfloren SN", manufactured by Nicca Chemical Industries, Ltd.): 4.5% by mass
<Antifoaming agent> Alcohol-based (product name "Antifoaming agent", manufactured by Furukawa Chemical Industry Co., Ltd., component: higher alcohol): 2.5% by mass
<Preservatives> Product name "Neoguard" (manufactured by Furukawa Chemical Industry Co., Ltd.): 0.5% by mass
Glycerin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.5% by mass
Water: balance. The ink used was a black dispersion ink manufactured by Toshin Kogyo Co., Ltd.
The steaming treatment and washing treatment after printing were carried out in the same manner as in Examples 1-9 and Comparative Examples 1-6.

[Evaluation test]
The evaluation fabrics that had been ink-jet printed after the pretreatment in each example were subjected to the following evaluations. The results are shown in Table 1.

＜Bleeding＞
The ink bleeding resistance was evaluated as follows.
The bleeding was checked twice in total, once after the inkjet printing and before the steaming treatment, and once after the washing treatment. In both the first and second tests, the bleeding resistance was evaluated based on the appearance of the lattice intersections when the printed image pattern was visually observed from a position 30 cm away from the fabric. The evaluation criteria are shown below.
○: When the appearance of the intersections of the lattices was as clear as Reference Example 1 for both the first and second times. ×: When the appearance of the intersections of the lattices was as clear as Reference Example 1 for the first time, but was inferior to Reference Example 1 for the second time, and the intersections could not be confirmed. XX: When the appearance of the intersections of the lattices was inferior to Reference Example 1 for both the first and second times, and the intersections could not be confirmed, causing practical problems.

<Texture>
The fabric was folded by hand 10 times to check how it folded, and the feel was evaluated according to the following criteria.
○: Creases occurred less than 3 times △: Creases occurred 4 to 7 times ×: Creases occurred 8 or more times

<Color (yellowing or not)>
After the cleaning treatment, the area where the pretreatment agent was applied but no ink was applied was observed to confirm whether it had taken on a yellowish tinge. Two experiments were performed, and the color was evaluated according to the following criteria.
○: No yellowing was observed in either experiment when the experiment was performed twice. △: Yellowing was observed in either experiment when the experiment was performed twice. ×: Yellowing was observed in both experiments when the experiment was performed twice.

As shown in Table 1, in Examples 1 to 9, even when inkjet printing was performed without drying after pretreatment, the same resistance to bleeding as in Reference Example 1, in which inkjet printing was performed after drying after pretreatment, was obtained, and the texture and color were also good. On the other hand, in Comparative Examples 1 to 6, in which the adhesive did not contain a cellulose derivative, inkjet printing without drying resulted in poor bleeding, texture, or color.
As described above, in the present Examples and Comparative Examples, the content of the glue was adjusted so that the liquid viscosity of the pretreatment agent was 2000 mPa s or more. However, if the glue used in each Comparative Example had the same content (2.0 mass %) as in Example 1, the liquid viscosity of the pretreatment agent would be significantly lower than 2000 mPa s, and it is considered that pretreatment itself would not be possible to perform using the screen printing machine.

According to the present invention, in inkjet printing of fabric using a dye ink, the ink is applied without drying after application of a pretreatment agent, thereby achieving improved productivity, low costs, energy savings, and space savings without causing bleeding or impairing the texture or color.

Claims (11)

The present invention includes an N-vinylformamide cationic polymer and a sizing agent,
The pretreatment agent for ink-jet textile printing, wherein the paste contains a cellulose derivative. The inkjet printing pretreatment agent according to claim 1, wherein the cellulose derivative is methylcellulose. The inkjet printing pretreatment agent according to claim 1 or 2, wherein the content ratio (mass ratio) of the paste to the N-vinylformamide cationic polymer is 1.0 or more and 15.0 or less. The inkjet printing pretreatment agent according to claim 1 or 2, wherein the content of the N-vinylformamide cationic polymer is 0.1% by mass or more and 5.0% by mass or less in a total mass (100% by mass) of the inkjet printing pretreatment agent. The inkjet printing pretreatment agent according to claim 1 or 2, wherein the content of the cellulose derivative is 0.5% by mass or more and 5.0% by mass or less in a total mass (100% by mass) of the inkjet printing pretreatment agent. The inkjet printing pretreatment agent according to claim 1 or 2, which contains the cellulose derivative as a first paste and further contains an inorganic compound as a second paste. The inkjet printing pretreatment agent according to claim 6, wherein the inorganic compound is montmorillonite. The inkjet printing pretreatment agent according to claim 1 or 2, further comprising a defoaming agent. The inkjet printing pretreatment agent according to claim 1 or 2, wherein the N-vinylformamide cationic polymer contains at least one selected from the group consisting of polyamidines and polyvinylamines. An inkjet printing method comprising pretreating a fabric with the inkjet printing pretreatment agent according to claim 1 or 2, and inkjet printing the pretreated area of the pretreated fabric without drying the pretreated fabric. The ink-jet printing method according to claim 10, wherein the ink used in the ink-jet printing is a disperse dye.