JP7042664B2 - Fiber pretreatment method - Google Patents

Description

The present invention relates to pretreatment inks, particularly pretreatment inks used for fibers, and pretreatment methods for fibers using the same.

Conventionally, hand-painting and screen printing have been the mainstream in textile printing methods. However, recently, a printing method using an inkjet printer (inkjet printing) is often used.

Examples of the colorant used for inkjet printing include water-soluble dyes. Such dyes have a clear hue and a wide color gamut that can be reproduced. On the other hand, the water-soluble dye has a low light resistance, and has a drawback that the fixing after the dye is attached to the fiber, the steps such as washing with water, and the treatment of the dye waste liquid generated by washing with water are complicated. For this reason, attention is being paid to the use of water-insoluble colorants instead of water-soluble dyes.

A white ink containing a white pigment is used as a water-insoluble colorant, and a white ink is adhered to fibers other than white to form a white base, and then the color ink is applied to an inkjet printer so as to overlap at least a part of the base. The printing method of adhering with is known. In such a printing method, a method of pretreating the fibers before adhering the white ink with the pretreatment ink is common. However, as a pretreatment agent contained in the pretreatment ink, for example, a cationic polymer (cationic resin) having an ammonium salt structure in the molecule is known. Although the cationic polymer has good performance as a pretreatment agent, the storage stability of the pretreatment ink containing the cationic polymer is poor, and improvement thereof is strongly desired.

Japanese Unexamined Patent Publication No. 07-119047 Japanese Unexamined Patent Publication No. 2000-226781

An object of the present invention is to provide a pretreated ink containing a cationic polymer and having good storage stability.

As a result of diligent studies, the present inventors have found that a cationic polymer containing a structural unit represented by a specific formula (1) in the molecule, an anionic resin, and a pretreated ink containing a specific surfactant have been obtained. The present invention has been completed by finding that the above problems can be solved.
That is, the present invention relates to the following 1) to 5).

1)
A pretreated ink containing a cationic polymer containing a structural unit represented by the following formula (1) in the molecule, an anionic resin, and polyoxyC2-C4 alkylene glycol.
A pretreatment ink in which the number of oxy-C2 alkylene groups is less than 50% of the total number of oxy-C2-C4 alkylene groups in the polyoxy-C2-C4 alkylene glycol.

[In equation (1),
R ¹ and R ² each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group.
X represents a halogen atom
n represents an integer of 1 or more. ]
2)
The pretreated ink according to 1) above, wherein the content of the cationic polymer is 3 to 25% by mass with respect to the total mass of the pretreated ink.
3)
Anionic resins include (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, urethane, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole. , Vinyl imidazole, and a polymer of one or more monomers selected from vinylidene chloride; a fluororesin; and a compound selected from natural resins, according to 1) above.
4)
The pretreatment ink according to 1) above, wherein the anionic resin is a compound selected from (meth) acrylic resin, styrene- (meth) acrylic resin, (meth) acrylic-urethane resin, and urethane resin.
5)
The pretreatment ink according to any one of 1), 3) and 4) above, wherein the content of the anionic resin is 1 to 5% by mass with respect to the total mass of the pretreatment ink.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a pretreated ink containing a cationic polymer and having good storage stability.

In the present specification, unless otherwise specified, "parts" and "%" including examples and the like are both described on a mass basis.

[Cation polymer]
The cationic polymer contains the structural unit represented by the formula (1) in the molecule. The cationic polymer can be obtained, for example, by reacting a secondary amine represented by "R ¹ R ² NH" with epihalohydrin, as described in JP-A-6-92012.
In the formula (1), examples of the alkyl group in R ¹ and R ² include a straight chain, a branched chain, and a cyclic alkyl group. Among these, a linear or branched-chain alkyl group is preferable, and a linear alkyl group is more preferable. The range of the number of carbon atoms of the alkyl group is not particularly limited, but is usually C1-C18, preferably C1-C8, more preferably C1-C4, still more preferably C1-C3, and particularly preferably C1 or C2.
Specific examples thereof include linear alkyl groups such as methyl, ethyl, n-propyl and n-butyl; branched chain alkyl groups such as isopropyl, isobutyl, sec-butyl and t-butyl; cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. , Cyclic alkyl group such as cyclooctyl and the like.

Examples of the aryl group in R ¹ and R ² include C6-C14, preferably C6-C10, and more preferably phenyl, which have a carbon number range of C6-C14. Specific examples thereof include phenyl, 1-naphthyl, 2-naphthyl and the like.

R ¹ and R ² can be bonded to form a ring to form a 5- or 6-membered heterocyclic group having a nitrogen atom as a ring-constituting atom. This heterocyclic group may further have one atom selected from an oxygen atom and a sulfur atom as a ring-constituting atom. Specific examples thereof include piperidine, pyrrolidine, pyrrole, morpholine, thiomorpholine and the like.
Further, the heterocyclic group can have a condensed ring structure together with two adjacent carbon atoms and also a carbon atom of C4-C8. Specific examples thereof include indole, indoline, carbazole, tetrahydroquinoline, tetrahydroisoquinoline and the like.
Of the above, alkyl groups are preferable as R ¹ and R ² .

In the formula (1), examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom is preferred.
Since n varies depending on the types of R ¹ and R ² , it is difficult to unconditionally determine it. As a guide, it is usually an integer of 1 or more, preferably 3 to 85, and more preferably about 5 to 80.

The weight average molecular weight of the cationic polymer is usually 500 to 30,000, preferably 750 to 20,000, and more preferably 1,000 to 10,000. Within such a range, the miscibility of the pretreated ink with other components, the water resistance of the pretreated fabric, the washing fastness, and the like can be improved.

The content of the cationic polymer with respect to the total mass of the pretreated ink is usually 3 to 25%, preferably 5 to 20%, and more preferably 5 to 15%. By setting this content, strike-through and whiteness tend to be good.

[Anionic resin]
Examples of the anionic resin include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, cyanoacrylate, (meth) acrylamide, olefin, styrene, urethane, vinyl acetate, vinyl chloride, vinyl alcohol, and vinyl ether. , A polymer of one or more monomers selected from vinylpyrrolidone, vinylpyridine, vinylcarbazole, vinylimidazole, and vinylidene chloride; fluororesins; and compounds selected from natural resins.
Examples of the polymer include known polymers such as random copolymers, block copolymers, alternating copolymers, and graft copolymers.
In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid, and (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester, and other terms are used. Is the same.

Among the above, as the anionic resin, a resin selected from (meth) acrylic resin, styrene- (meth) acrylic resin, (meth) acrylic-urethane resin, and urethane resin is preferable; (meth) acrylic resin, styrene-. A resin selected from (meth) acrylic resin and urethane resin is more preferable. By using these anionic resins, the color unevenness of the base set by the white ink is suppressed, and the abrasion resistance after printing and the washing fastness tend to be improved.
Examples of the urethane resin include polyether urethane resin, polyester urethane resin, polycarbonate urethane resin and the like.

The content of the anionic resin with respect to the total mass of the pretreated ink is usually 1 to 5%, preferably 1.5 to 5%. By setting such a content, it is possible to prevent color unevenness when printing white ink and reduce traces of pretreated ink.

The anionic resin can be obtained by a known material and production method. It can also be purchased as a resin emulsion or the like.
Examples of commercially available products of the (meth) acrylic resin and styrene- (meth) acrylic resin include Movinyl 952A (Tg = -38 ° C., solid content 45%) and 710A (Tg =) manufactured by Japan Coating Resin Co., Ltd. 9 ° C., solid content 41%, viscosity 200-700 mPa · s, MFT = 0 ° C.; (meth) acrylic resin), 718A (Tg = -6 ° C., solid content 45%, viscosity 500 mPa · s or less, MFT = 0 ° C. ((Meta) acrylic resin), 6960 (Tg = -23 ° C, solid content 45%, viscosity 100-1200 mPa · s, MFT = 0 ° C; styrene- (meth) acrylic resin), 7320 (Tg = -20 ° C, Solid content 45%, viscosity 100 mPa · s or less, MFT = 0 ° C; (meth) acrylic resin), 7400 (Tg = −41 ° C, solid content 50%, viscosity 100-2500 mPa · s, MFT = 0 ° C; (meth) ) Acrylic resin), 7420 (Tg = −26 ° C., solid content 50%, viscosity 100-2500 mPa · s, MFT = 0 ° C.; (meth) acrylic resin), 966A (Tg = −32 ° C., solid content 45%, Viscosm 300 mPa · s or less, MFT = 0 ° C; styrene- (meth) acrylic resin); Microgel E-1002, E-5002 manufactured by Nippon Paint Co., Ltd .; Boncoat 4001, 5454 manufactured by DIC Corporation; Nippon Zeon Co., Ltd. SAE 1014 manufactured by SAE 1014; Cybinol SK-200 manufactured by Saiden Chemical Corporation; John Krill 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, manufactured by BASF. 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610; NK binder R-5HN (solid content 44) manufactured by Shin-Nakamura Chemical Co., Ltd. %) And the like.

Examples of commercially available (meth) acrylic-urethane resins include Movinyl 6910 manufactured by Japan Coating Resin Co., Ltd., Hybrid Emulsion X-216-854E-1, X-216-854E-2 manufactured by Saiden Chemical Co., Ltd., and the like. Can be mentioned.
Examples of commercially available urethane resins include Sancure 2710 manufactured by Japan Lubrizol Co., Ltd .; Permarin UA-150 manufactured by Sanyo Kasei Kogyo Co., Ltd. (; Superflex 460, 470, 610 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). 700; NeoRez R-9660, R-9637, R-940 manufactured by Kusumoto Kasei Co., Ltd .; Adeka Bontita HUX-380, 290K manufactured by ADEKA Corporation; Takelac W-605, W-635 manufactured by Mitsui Chemicals Co., Ltd. WS-6021; Polyether (Tg = 20 ° C.) manufactured by Taisei Fine Chemical Co., Ltd. and the like can be mentioned.

The glass transition temperature (Tg) of the anionic resin is usually −60 ° C. to 40 ° C., preferably −50 ° C. to 30 ° C., more preferably −45 ° C. to 25 ° C., still more preferably −43 ° C. to 20 ° C. By setting it in such a range, the texture of the fabric after the pretreatment, for example, the touch of the cloth can be improved.

Further, for the purpose of improving the breaking, cracking, washing fastness, and abrasion resistance of the image printed on the fabric, the breaking point elongation of the anionic resin is 200 to 500%, and the elastic modulus is 20 to 400 MPa. The degree is preferable.
The breaking point elongation is a value obtained by preparing a film having a thickness of about 60 μm from an anionic resin using a known method and measuring under the conditions of a tensile test gauge length of 20 mm and a tensile speed of 100 mm / min. ..
Similarly, for the elastic modulus, a film having a thickness of about 60 μm is formed from an anionic resin, molded into a tensile test dumbbell having a parallel portion width of 10 mm and a length of 40 mm, and a tensile test is performed in accordance with JIS K7161: 1994. Let it be the tensile elastic modulus obtained by going.

The D50 of the anionic resin is usually 30 to 300 nm, preferably 80 to 300 nm. By setting D50 as such, the dispersibility of the anionic resin in the pretreated ink can be improved.
Further, for the purpose of improving the abrasion resistance of the colored image after printing on the fabric, it is preferable to set the lower limit value of D50 to about 100 nm.

[Surfactant]
The pretreated ink preferably further contains a surfactant. The type of the surfactant is not particularly limited, but for example, a surfactant selected from acetylene glycol and polyalkylene glycol is preferable. By containing the surfactant, the increase in the viscosity of the pretreated ink, the aggregation of the components and the like are suppressed, and the storage stability is improved.
Among the above, the pretreated ink containing at least polyalkylene glycol as a surfactant tends to further improve the whiteness of the base and the strike-through.

Examples of the acetylene glycol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7-. Surfactants selected from diols, 2,4-dimethyl-5-decyne-4-ol, and 2,4-dimethyl-5-decyne-4-ol or alkylene oxide adducts thereof are preferred. Examples of the alkylene oxide include those selected from C2-C4 straight chain, branched chain, and cyclic alkylene oxides. Of these, straight chain or branched chain alkylene oxides are preferred.
Examples of such a surfactant include the Orfin series (104, E1010, etc.) manufactured by Air Products Co., Ltd. and the Surfinol series (440, 465, 61, etc.) manufactured by Nisshin Kagaku Kogyo Co., Ltd.

As the polyalkylene glycol surfactant, for example, a surfactant selected from polyoxyethylene alkyl ether, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polyoxy C2-C4 alkylene glycol is preferable. Among these, polyoxyC2-C4 alkylene glycol is preferable.

Examples of the polyoxyethylene alkyl ether include polyoxyalkylene branched decyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene isodecyl ether, and polyoxyalkylene lauryl ether.
Examples of commercial products include Neugen XL-40, 50, 60, 70, 80, 100, 140, 160, Neugen TDS-30, 50, 70, 80, 90, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. 100, 120 and the like can be mentioned.
Examples of the fatty acid ethylene oxide adduct include stearic acid ethylene oxide adduct and polyethylene glycol lauric acid ester. Examples of the commercially available product include Emanone 1112, 3199V, 3299V, 3299VR, 3201M-V manufactured by Kao Corporation.
Examples of commercially available products of the higher alkylamine ethylene oxide adduct include Amit 102, 105, 105A, 302, 320 manufactured by Kao Corporation.
Examples of commercially available products of polyoxy C2-C4 alkylene glycol are, for example, Emargen PP-290 (polyethylene glycol / polypropylene glycol 160/30 copolymer) manufactured by Kao Co., Ltd .; New Pole PE-manufactured by Sanyo Kasei Kogyo Co., Ltd. 61, PE-62, PE-64, PE-68, PE-71, PE-74, PE-75, PE-78, PE-108 (polyoxyethylene polyoxypropylene block polymer); Daiichi Kogyo Seiyaku Co., Ltd. Epan 410, 420, 450, 485, 680, 710, 720, 740, 750, 785, U-103, U-105, U-108 (polypropylene glycol has a weight average molecular weight of about 950 to 4000, polyoxyethylene). Polyoxyethylene polyoxypropylene glycol) having a content of about 5 to 95%.
As the polyoxyC2-C4 alkylene glycol, polyoxyC2-C3 alkylene glycol is preferable, and polyoxyethylene polyoxypropylene glycol is more preferable.
Further, the number of oxy-C2 alkylene groups in the total number of oxy-C2-C4 alkylene groups in the polyoxy-C2-C4 alkylene glycol is usually smaller than 50%, preferably 15 to 45%, and more preferably 20 to 40%. As an example, when the total number of bonds of the oxyC2 alkylene group, the oxy C3 alkylene group, and the oxy C4 alkylene group is 10, the number of bonds of the oxyalkylene group is smaller than 5. The number of bonds of the oxy-C2-C4 alkylene group is an average value.
When the polyoxyC3-C4alkylene group is a hydrophobic group and the polyoxyC2 alkylene group is a hydrophilic group among the polyoxyalkylene glycols, the weight average molecular weight of the hydrophobic group is usually 2250 to 4000, preferably 2750 to 3600. ..
Examples of those satisfying both the content of the oxyC2 alkylene group and the weight average molecular weight of the hydrophobic group include Epan U-103.
The pretreated ink containing the cationic polymer can improve the storage stability by containing such a surfactant.

The content of the surfactant with respect to the total mass of the pretreated ink is usually 0.05 to 5%, preferably 0.05 to 3%, more preferably 0.05 to 1%, still more preferably 0.1 to 0. It is about 5.5%. With such a content, the printed fibers tend to have excellent washing fastness and abrasion resistance. In addition, the storage stability of the pretreated ink tends to be excellent.

[Ink preparation]
The pretreated ink may further contain an ink adjusting agent, if necessary.
Examples of the ink preparation agent include a fungicide, a preservative, a pH adjuster, a chelating reagent, a rust preventive, a water-soluble ultraviolet absorber, a water-soluble polymer compound, an antioxidant, a glue, and the like.

Specific examples of the fungicide include sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. ..

Examples of preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloaryl sulfone-based, iodopropagil-based, haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzothiazole. System, isothiazoline system, dithiol system, pyridine oxide system, nitropropane system, organic tin system, phenol system, tetraammonium salt system, triazine system, thiazine system, anilide system, adamantan system, dithiocarbamate system, brominated indanone system, Examples thereof include benzyl bromacetate-based compounds and inorganic salt-based compounds.
Specific examples of the organic halogen-based compound include sodium pentachlorophenol. Specific examples of the pyridine oxide compound include 2-pyridinethiol-1-oxide sodium. Specific examples of the isothiazolinone compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl-4-isothiazolin-3-one. On, 5-chloro-2-methyl-4-isothiazolin-3-onmagnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-oncalc chloride, 2-methyl-4-isothiazolin-3-oncalcium Chloride and the like can be mentioned.
Specific examples of other antiseptic and antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, manufactured by Arch Chemical Co., Ltd., trade names Proxel GXL (S), Proxel XL-2 (S) and the like.

As the pH adjuster, any substance can be used as long as the pH of the ink can be controlled in the range of, for example, 5 to 11 without adversely affecting the prepared ink. Examples of the pH adjuster include alkali metal hydroxides, alkaline earth metal hydroxides, aliphatic amine compounds and alcohol amine compounds.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide. Examples of the hydroxide of the alkaline earth metal include beryllium hydroxide, magnesium hydroxide, calcium hydroxide and strontium hydroxide. Among these, hydroxides of alkaline earth metals are preferable, and lithium hydroxide and sodium hydroxide are more preferable.
Examples of the aliphatic amine compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, dimethylamine and trimethylamine, and ammonia or triethylamine is preferable.
Examples of the alcohol amine compound include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylethanolamine, dimethylethanolamine and N-methyldiethanolamine, and a tertiary amine is preferable. Kind, more preferably triethanolamine.
Other specific examples include, for example, carbonates of alkali metals such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; disodium phosphate and the like. Phosphate; etc.

Specific examples of the chelating reagent include disodium ethylenediamine tetraacetate, sodium nitrilo triacetate, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

Specific examples of the rust preventive include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

Specific examples of the water-soluble ultraviolet absorber include sulfonated benzophenone-based compounds, benzotriazol-based compounds, salicylic acid-based compounds, cinnamic acid-based compounds, and triazine-based compounds.

Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines, polyimines and the like.

As the antioxidant, for example, various organic and metal complex-based anti-fading agents can be used. Specific examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocycles and the like. Will be.

[Adhesive]
The pretreated ink may further contain an adhesive, if necessary. Examples of the sizing agent include starches such as corn and wheat; cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose; polysaccharides such as sodium alginate, arabia gum, locust bean gum, tranth gum, guar gum, and tamarind seeds, gelatin, and casein. Examples include synthetic water-soluble polymer compounds containing proteins; natural water-soluble polymers such as tannin and lignin; and polyvinyl alcohol, polyethylene oxide, (meth) acrylic acid, maleic anhydride and the like.
The content of the adhesive is usually about 0 to 20% with respect to the total mass of the pretreated ink.

The pretreated ink is preferably used for fibers. The fiber is not particularly limited. Examples thereof include natural fibers such as silk, cotton, wool, nylon, polyester and rayon, fibers selected from the group consisting of synthetic fibers, or blended fibers thereof. Among these, cotton and a blended fiber containing cotton are preferable.

[Pretreatment method]
The pretreatment method is a pretreatment method including a step of adhering the pretreatment ink to fibers. The step of adhering the pretreatment ink to the fiber is not particularly limited. Examples thereof include a step of implanting the fiber in the pretreated ink; and a step of applying or spraying the pretreated ink to the fiber.
In the above-mentioned fiber pretreatment method, the amount of the cationic polymer adhered to the pretreatment ink is usually 2 to 6 mg / cm ² , preferably 2.5 to 5.5 mg / cm ² with respect to the fiber in terms of solid content. , More preferably, it is a method of adhering the pretreated ink to the fiber so as to be 3 to 5 mg / cm ² . With such an adhesion amount, the whiteness when the white base is placed on the fiber is high, and the feel of the fiber is good.

After adhering the pretreatment ink to the fibers, the fibers can be dried, if desired. The fibers can be dried at 110 to 200 ° C., preferably 120 to 180 ° C. for several minutes. By setting the heating temperature to 110 ° C. or higher, the fixability of the components contained in the pretreated ink to the fibers becomes good. Further, by setting the heating temperature to 200 ° C. or lower, deterioration of the components contained in the fiber and the pretreatment ink due to heat can be prevented.

As for all the above-mentioned components and the like, one of them can be used alone, or two or more of them can be used in combination.
For all the above-mentioned matters, the combination of preferable ones is more preferable, and the combination of more preferable ones is further preferable. The same applies to the preferable and more preferable ones, and the combination of the more preferable one and the more preferable one.

By pretreating the fibers with the pretreatment ink, it is possible to suppress fluffing of the fibers in addition to the above effects. Therefore, an image having excellent sharpness can be obtained both when a white base is provided on the pretreated fiber and when an image is printed on the base with color ink. Further, by improving the fixing property of the image printed on the pretreated portion, the scratch resistance and the washing fastness of the image can be improved.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
"Water" used in the examples means "ion-exchanged water" unless otherwise specified.
When the solid content of the liquid was measured, it was determined by the dry weight method using MS-70 manufactured by A & D Co., Ltd.

[Preparation of pretreatment ink]
Each component shown in Table 1 below was mixed to make a total amount of 100 parts, and then sufficiently stirred and mixed to obtain pretreated inks of Example 1 and Comparative Examples 1 to 3.
The numerical values in Table 1 below mean "parts" and are solid content conversion values.

The abbreviations and the like in Table 1 below have the following meanings.
KHE100L: Unisense KHE100L (dimethylamine / ammonia / epichlorohydrin polycondensate, solid content 60%), a cationic polymer manufactured by Senka Co., Ltd.
AR1: Anionic resin manufactured by Japan Coating Resin Co., Ltd., Movinyl 6960 (styrene / acrylic resin emulsion, solid content 45%, Tg = -23 ° C).
U103: Epan U-103, EO content 30%.
U105: Epan U-105, EO content 50%.
750: Epan 750, EO content 50%.
PP-290: Emargen PP-290, EO content 84%.

[Evaluation of stability]
The pretreatment inks of Examples and Comparative Examples were placed in a transparent container (Iboy wide mouth 100 mL) and shaken up and down by hand 30 times, and then it was visually observed whether or not deposits were formed on the container. The evaluation results are shown in Table 1.
A: No deposits were found on the wall surface or bottom of the container after shaking.
B: Solid deposits were observed on the wall surface or bottom of the container after shaking.
C: A large amount of solid adhered to the container wall surface or the container bottom after shaking.

From the results in Table 1 above, it was found that the pretreated ink using the surfactant of the example was extremely excellent in stability as compared with the pretreated ink of the comparative example.

The pretreatment ink of the present invention contains a cationic polymer and has good storage stability, so that it is extremely useful as a pretreatment ink for fibers.

Claims (5)

A pretreated ink containing a cationic polymer containing a structural unit represented by the following formula (1) in a molecule, an anionic resin, and polyoxy C2-C4 alkylene glycol, wherein the polyoxy C2-C4 alkylene glycol is used. A pretreated ink in which the number of oxyC2 alkylene groups is 15 to 45% of the total number of oxyC2-C4 alkylene groups in the ink.

[In formula (1), R ¹ and R ² each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group.
X represents a halogen atom
n represents an integer of 1 or more. ] The pretreatment ink according to claim 1, wherein the content of the cationic polymer is 3 to 25% by mass with respect to the total mass of the pretreatment ink. Anionic resins include (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, cyanoacrylate, acrylamide, olefin, styrene, urethane, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinylpyrrolidone, vinylpyridine, vinylcarbazole. , Vinyl imidazole, and a polymer of one or more monomers selected from vinylidene chloride; fluororesin; and a compound selected from natural resins, according to claim 1. The pretreatment ink according to claim 1, wherein the anionic resin is a compound selected from (meth) acrylic resin, styrene- (meth) acrylic resin, (meth) acrylic-urethane resin, and urethane resin. The pretreatment ink according to any one of claims 1, 3 and 4, wherein the content of the anionic resin is 1 to 5% by mass with respect to the total mass of the pretreatment ink.