WO2022173124A1 - Pretreatment solution composition for inkjet pigment textile printing and pretreatment method using same - Google Patents

Abstract

The present invention relates to a pretreatment solution composition for inkjet pigment textile printing and a pretreatment method using same. Particularly, the present invention relates to a pretreatment solution composition comprising: (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; and (d) water, and a pretreatment method comprising preparing a pretreatment solution composition for inkjet pigment textile printing by mixing (a) a cationic compound, (b) a resin dispersion, (c) a crosslinking agent, and (d) water, and applying the composition onto fabric. A pretreatment solution composition for formaldehyde-free inkjet pigment textile printing, according to the present invention, can be used in particularly textile products for infants.

Description

Pretreatment liquid composition for inkjet pigment printing and pretreatment method using the same

The present invention relates to a pretreatment composition for inkjet pigment printing and a pretreatment method using the same. Specifically, the present invention relates to (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; and (d) water, particularly the use of said pretreatment composition in inkjet pigment printing.

Compared to the traditional textile printing method such as screen printing, the digital inkjet printing method has a great advantage in that a multi-colored image can be easily implemented on media using computer software such as RIP. In particular, its importance is being emphasized as it has the advantages of low manpower required for printing, unlimited installation space, low wastewater generation, low operating cost, and small batch production.

Colorants used in printing include dyes (reactive dyes, acid dyes, disperse dyes, etc.) and pigments. Among them, pigment printing is economically advantageous because it does not depend on the selectivity of the fabric compared to dyes or other colorants, and the cost of water and energy required for fixing or washing process is small.

However, inkjet pigment printing, which is printed on fabric by mixing pigment and resin, is required to improve fastness and color development compared to inkjet dye printing.

A method of physically fixing the pigment to the fabric surface using a pretreatment solution is known for the purpose of improving the color fastness and color development of the inkjet pigment printing, but this method affects the texture of the fabric (JP 2009-299240 Publication, US Publication) See Publication No. 8,784,508, JP 2008-266853). Accordingly, while maintaining the texture of the fabric, additional fastness (especially, fastness to friction) and improvement of color development are required.

Accordingly, the present inventors intend to provide a pretreatment solution composition for inkjet pigment printing capable of obtaining a printed material having excellent fastness and color development by solving the above-described problems.

In addition, the pretreatment liquid composition for inkjet printing according to the present invention is applicable to infant clothing.

It is an object of the present invention: (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; And (c) to provide a pretreatment solution composition for inkjet pigment printing comprising water.

Another object of the present invention is (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; And (c) to provide a pretreatment method comprising mixing water to prepare a pretreatment solution composition for inkjet pigment printing and applying to the fabric.

In order to achieve the above object, the present invention is (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; And (d) provides a pretreatment composition for inkjet pigment printing comprising water.

The present invention also relates to: (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; And (c) it provides a pretreatment method comprising mixing water to prepare a pretreatment solution composition for inkjet pigment printing and applying to the fabric.

The cationic compound attached to the fabric by the treatment of the pretreatment composition for inkjet pigment printing according to the present invention improves color development by inhibiting the penetration of the ink into the fabric, and the resin dispersion and crosslinking agent improve the fastness of the printed material by heat treatment ( especially the fastness to friction).

In addition, the pretreatment liquid composition for inkjet pigment printing according to the present invention is formaldehyde-free and harmless to the human body, so it can be used for clothes and textiles for infants.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

The present invention in one aspect, (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; And (d) relates to a pretreatment composition for inkjet pigment printing comprising water.

In the present invention, the cationic compound may be a polyvalent metal compound, an organic acid, or a cationic resin.

In the present invention, the cationic compound may contain one of calcium nitrate and calcium chloride.

In the present invention, the resin dispersion may be a nonionic or cationic urethane-based or acrylic-based binder resin.

The crosslinking agent used in the present invention may be a formaldehyde-free compound comprising at least one reactive group selected from the group consisting of epoxy, carbodiimide, and oxazoline.

In the present invention, with respect to 100% by mass of the pretreatment composition, 0.25 to 2% by mass of the cationic compound, 0.5 to 5% by mass or less of the resin dispersion, 1 to 10% by mass of the crosslinking agent, and the remaining amount of water.

In another aspect of the present invention, (a) a cationic compound; (b) a resin dispersion; (c) a crosslinking agent; and (c) mixing with water to prepare a pretreatment composition for inkjet pigment printing and applying it to a fabric.

In the present invention, the fabric may be selected from natural fibers, blend fibers or synthetic fibers.

In the present invention, the pretreatment composition for inkjet pigment printing may be applied to the fabric by a method selected from padding application, roller application, spray application, or inkjet application.

As used herein, the term "composition" is intended to include not only products comprising the specified ingredients, but also any products made directly or indirectly by combining the specified ingredients.

Hereinafter, the pretreatment composition for inkjet pigment printing of the present invention and a pretreatment method using the same will be described in detail.

cationic compound

The cationic compound used in the present invention may be a polyvalent metal compound, an organic acid, or a cationic resin. In particular, the use of a polyvalent metal compound is preferable in that the stability of the pretreatment composition is good, and a printed material having excellent color development can be obtained because non-uniformity does not occur during printing. The polyvalent metal compound acts to form a film on the fabric by depositing a water-dispersible resin (resin emulsion) while aggregating the pigment in the ink.

Examples of the polyvalent metal compound include a titanium compound, a chromium compound, a copper compound, a cobalt compound, a strontium compound, a barium compound, an iron compound, an aluminum compound, a calcium compound, a magnesium compound, or a salt form thereof (a polyvalent metal salt). . Among these polyvalent metal compounds, those preferred from the viewpoint of efficient aggregation of pigments are, for example, composed of an aluminum compound, a magnesium compound, and a calcium compound, and more preferably composed of at least one of a calcium compound and a magnesium compound. It is a calcium compound. More specifically, the above-mentioned polyvalent metal compound is, for example, calcium carbonate, chalk, kaolin, calcined clay, talc, calcium nitrate, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, aluminum silicate, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, calcium montrolonite, sodium montmorillonite, bentonite and acrylic plastic pigments, and organic pigments such as polyethylene and polyurea there is A preferred pretreatment is a solution of a polyvalent cation salt such as calcium chloride, calcium acetate or calcium acetate tetrahydrate.

These polyvalent metal compounds may be used independently, or multiple types may be mixed and used for them.

It is preferable that this concentration in the pretreatment liquid composition of the polyvalent metal compound is in the range of 0.25 to 2 mass% from the viewpoint that the ink properly forms a film. When it is less than 0.25 mass %, improvement in color development cannot be expected, and when it exceeds 2 mass %, there is a problem of low friction fastness due to an excess of pigment.

resin dispersion

The resin dispersion used in the present invention is used in the pretreatment composition to form a film after printing to improve the abrasion resistance of the printed material and the fixing performance of the ink. The binder resin emulsion used as the resin dispersion of the present invention is usually, for example, acrylic, styrene-acrylic, fluorene, urethane, vinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene vinyl acetate, etc. can be used, In order to satisfy the color fastness and color development of the pigment through flexibility and film properties due to the high elongation at break, urethane-based and acrylic-based binder resins are preferable.

The urethane resin emulsion used in the present invention refers to an emulsion that is self-dispersed in an aqueous phase using a monomer including a hydrophilic functional group without using a surfactant during synthesis. This has an advantage in improving water resistance because there is no desorption of the surfactant due to moisture contact after printing.

The urethane resin emulsion is a resin emulsion containing a urethane bond in its molecular structure. Among them, the polyether type urethane resin has an ether bond in the main chain, the polyester type urethane resin has an ester bond in the main chain, and the polycarbonate type urethane resin has a carbonate bond in the main chain.

In addition, the urethane resin emulsion has an acid value in the range of 10 to 100 mg KOH/g. more preferably 15 to 50 mg KOH/g. A resin emulsion having an acid value of less than 100 mg KOH/g can preferably maintain the water resistance of the printed fabric. The resin emulsion having an acid value greater than 10 mg KOH/g has satisfactory storage stability and has high color and adhesion properties of ink printed on fabric.

The urethane resin emulsion prevents cracks or cracks in the image by binding the composition in the ink layer on the fabric surface after printing to increase the abrasion resistance and flexibility of the printed material. Therefore, the preferred elongation at break is in the range of 200 to 500%, and the preferred elastic modulus is in the range of 20 to 400 MPa.

The urethane resin emulsion has a preferred average particle size in the range of 30 to 300 nm, more preferably 80 to 300 nm. At the average particle size in the above range, the resin emulsion is uniformly dispersed in the pretreatment solution composition. The low average particle size value of the resin emulsion preferably improves the abrasion resistance of the printed material and imparts optical properties due to the larger specific surface area. In addition, the weight average molecular weight of the resin emulsion has a value of 2,000 to 200,000 g/mol. More preferably, it has a value of 5,000 to 100,000 g/mol.

Commercially available urethane resin emulsions available in view of the above-mentioned physical properties include, for example, SANCURE 2255, 20051 898, LUBRIJET T140 (commercial name, Lubrizol Corporation); PERMARIN UA-150, UCOAT UWS-145, UX-390 (commercial name, Sanyo Chemical); SUPERFLEXES 460, 470, 600, 610, 650, 700 (commercial name, Daiichi Kogyo Seiyaku), HYDRAN WLS-201, HYDRAN CP-7010, CP-702, CP-7030, CP-7060, CP-7610 ( Commercial name, DIC Corporation), NeoREzs R-9660, R-9637, R-940 (commercial name, Kusumoto Chemicals); ADEKA BONTIGHERs HUX-20, 350, 830, SPX-0672 (commercial name, ADEKA Corporation); TAKELAC W-6110, W-605, W-635, WS-6021 (commercial name, Mitsui Chemicals) and the like.

Further, examples of the acrylic cationic resin include MOWINYL 6901, 6951, 6940, 6950, 7820, 3500 (commercial name, Japan Coating Resin Corporation).

The resin dispersion used in the present invention is preferably a nonionic or cationic resin. Since it hardly reacts with other components of the pretreatment solution composition, it is possible to maintain stability over time of the pretreatment solution composition.

The resin dispersion used in the present invention can be preferably used in an amount of 0.5 to 5 mass% in the total pretreatment liquid composition (100 mass%). When it is less than 0.5 mass %, the friction fastness becomes low, and when it exceeds 5 mass %, the fastness increases, but it may become a cause of impairing the texture of a fabric.

crosslinking agent

The crosslinking agent used in the present invention is a crosslinking agent capable of reacting with a hydroxyl group with a salt form of carboxylate, sulfonate, or phosphonate, which is a crosslinking reactive group of a dispersant or resin dispersion in a pigment ink.

The crosslinking agent used in the present invention may include one or more reactive groups selected from the group consisting of epoxy, carbodiimide, and oxazoline.

The epoxy crosslinking agent is Nagase's Denacol series, the carbodiimide crosslinking agent is Nisshinbo's Carbodilite series, and the oxazoline crosslinking agent is Nippon Shokubai's EPOCROS WS series. It is particularly preferred to use an epoxy crosslinking agent.

In addition, the reactive group of the crosslinking agent used in the pretreatment composition may react with the hydroxyl group of the cotton or cotton blend fabric cellulose to improve the adhesion of the pigment, thereby improving the fastness of the pigment ink.

The crosslinking agent used in the present invention may be 0.1 to 10 mass% of the total pretreatment solution composition (100 mass%). Preferably it can be used in the range of 0.1-5 mass %.

Although the pretreatment liquid composition for inkjet pigment printing is an aqueous solution containing water, a water-soluble organic solvent may be added from the viewpoint of viscosity adjustment and moisturizing effect. The water-soluble organic solvent that can be used in the pretreatment composition is the same as the water-soluble organic solvent used by mixing with ink. When this water-soluble organic solvent is contained, it is preferable to add in the range of 0.1-20 mass % in the pretreatment liquid composition, and it is more preferable that it is the range of 0.5-10 mass %.

A pH adjuster, a fungicide, an antioxidant, a rust inhibitor, a chelating agent, etc. may be added to the pretreatment composition for inkjet pigment printing as needed.

Preparation of pretreatment solution composition

The pretreatment liquid composition for inkjet pigment printing can be prepared by dispersing and mixing each of the above components by an appropriate method. After sufficiently stirring each of the above components, the target pretreatment solution composition can be obtained by filtering to remove coarse particles and foreign substances that cause clogging.

pretreatment process

As a method of attaching the pretreatment solution composition to the fabric, for example, a method of immersing the fabric in the pretreatment solution composition (padding application), a method of applying the pretreatment solution composition with a roll coater, etc. (roller application), spraying the pretreatment solution composition with a spray device, etc. The method of spraying by the inkjet method (spray application|coating), the method of injecting the pretreatment liquid composition by an inkjet system (inkjet application|coating), etc. are mentioned, Any method may be used.

textile

The material constituting the fabric is not particularly limited, and for example, natural fibers such as cotton, wool, silk, hemp, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, polyurethane, or natural fibers It can be used for blended fibers mixed with synthetic fibers.

[Example]

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Example 1: Preparation of ink composition

By using the pigment dispersion, the resin dispersion, and other additives, an inkjet pigment ink composition (1) was prepared with a composition as shown in Table 1 below.

Table 1

[Carbon black (black pigment dispersion dispersed with anionic polymer dispersant, particle size 100nm, Inktech), UCOAT UX-390 (polycarbonate-based polyurethane, Sanyo Chemical); 1,2-hexanediol (Camptrose); glycerin (LG Household & Health Care); BYK-348 (polyether-modified siloxane, BYK); BT550 (1,2-benzisothiazolin-3-one, CDI)].

Example 2: Preparation of pretreatment liquid composition and evaluation of properties

Using a cationic compound, a resin dispersion, and a crosslinking agent, a pretreatment solution composition for inkjet pigment printing [Examples (1) to (6), Comparative Examples (2) to (5)] with a composition as shown in Table 2 below prepared [calcium chloride (Duksan Pure Chemical), Mowinyl 6901 (cationic styrene acrylic resin, Japan Coating Resin Corp.) SUPERFLEX 500M (nonionic self-emulsifying urethane resin, Daiichi Kogyo Chemical Co., Ltd.)); Denacol EX-512, Denacol EX-821 (epoxy crosslinking agent, Nagase Chemtex); EPOCROS WS-700 (oxazoline crosslinking agent, Nippon Shokubai)].

Table 2

Table 3

After padding the pretreatment solution composition of Examples (1) to (6) and Comparative Examples (2) to (5) on a plain fabric with 40 cotton, the ink composition (1) was printed in a single color with an industrial printer equipped with XaarHead5501, It was output in resolution 720X720, 4pass. After hot-pressing at 180° C. for 3 minutes, evaluation of the printed product was performed.

Friction fastness

The evaluation was conducted in accordance with KSK ISO 105-X12: 2016 (chronometer method), and the degree of contamination was determined by the standard gray color table, and grades 1 to 5 were indicated, with grade 5 being the best.

A: Friction fastness 4 or more

B: Friction fastness 3 or more but less than 4

C: Friction fastness 2 or more and less than 3

D: friction fastness less than 2

chromogenic

The color development of the printed product was evaluated by visually discriminating.

A: No blurring is observed at all.

B: A blurry part is observed partially.

touch

Sensory evaluation was performed for the tactile sense of the printed product.

A: The original texture of the fabric is maintained, and the softness of the fabric remains intact.

B: The original texture of the fabric is slightly damaged, and the fabric is slightly hard.

C: The original texture of the fabric is damaged, and the fabric is hard.

The cotton printouts treated with the pretreatment composition of Examples (1) to (6) had excellent color development and tactile feel, and in particular, Examples (1) to (6) were also excellent in friction fastness.

On the other hand, Comparative Example (1), which was not pre-treated, showed poor rub fastness and color development, and when treated with the pre-treatment composition of Comparative Example (2), no cationic compound was added, so there was no improvement in color development. and, when treated with the pretreatment composition of Comparative Example (3), the cationic compound was added in excess and the ink did not penetrate into the fibers, so the color development was excellent, but due to the excess pigment on the surface, it showed low fastness to friction. In addition, when treated with the pretreatment solution composition of Comparative Example (4), the friction fastness was low because no resin dispersion was added. It was very stiff.

As described above, the pretreatment composition for inkjet pigment printing of the present invention has excellent color development and fastness of the inkjet pigment printing material while maintaining the texture of the fabric, so that high-quality output can be obtained.

As described above in detail a specific part of the content of the present invention, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and it is clear that the scope of the present invention is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (8)

1. A pretreatment composition for inkjet pigment printing comprising:

   (a) cationic compounds;

   (b) a resin dispersion;

   (c) a crosslinking agent; and

   (c) water.
2. According to claim 1,

   The cationic compound is a polyvalent metal compound, an organic acid or a cationic resin, characterized in that the inkjet pigment printing pretreatment composition.
3. According to claim 1,

   The resin dispersion is a nonionic or cationic urethane or acrylic binder resin, characterized in that the inkjet pigment printing pretreatment composition.
4. The method of claim 1,

   The crosslinking agent is a pretreatment composition for inkjet pigment printing, characterized in that it comprises at least one reactive group selected from the group consisting of epoxy, carbodiimide, and oxazoline.
5. According to claim 1,

   With respect to 100% by mass of the pretreatment composition, 0.25 to 2% by mass of a cationic compound, 0.5 to 5% by mass or less of a resin dispersion, 1 to 10% by mass of a crosslinking agent, and the remaining amount of water, inkjet pigment printing pretreatment liquid composition.
6. A pretreatment method comprising preparing the pretreatment liquid composition for inkjet pigment printing according to any one of claims 1 to 5 and applying the composition to a fabric.
7. 7. The method of claim 6,

   The pretreatment method, characterized in that the fabric is selected from natural fibers, blend fibers or synthetic fibers.
8. 7. The method of claim 6,

   The pretreatment composition for inkjet pigment printing is a pretreatment method, characterized in that it is applied to the fabric by a method selected from padding application, roller application, spray application or inkjet application.