JPH05179577A - Fabric for ink-jet dyeing and method for dyeing - Google Patents

Abstract

PURPOSE:To obtain the subject cloth ink-jet dyeable in excellent sharpness, build-up properties and reproducibility by sticking a water-insoluble water absorbing resin having specific water absorption ability to fabric. CONSTITUTION:For example, a fiber material such as synthetic fiber or semi- synthetic fiber is provided with a water dispersion of a water-insoluble water absorbing resin having 500-1,000ml/g water absorption ability, such as partial hydrolyzate of crosslinked polyacrylamide or crosslinked acrylic acid-acrylamide copolymer to prepare ink-jet dyed fabric. Dye ink is added to the fabric by ink-jet method, the dye is thermally stuck to the fabric, which is subjected to reduction cleaning to give a high-grade printed material ink-jet dyeable in excellent sharpness, build-up properties and reproducibility.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cloth on which a dye ink is applied by an ink jet system to obtain a printed image having good sharpness and good build-up property.

[0002]

2. Description of the Related Art Recently, ink jet type pattern dyeing has been developed in the textile printing field. That is, the original pattern is read by a sensor, processed by a computer, converted into an electric signal, and a dye solution is ejected from an inkjet nozzle to print or dye on a cloth. However, in the dyeing by the inkjet method, "bleeding" occurs when the dye ink is printed on the cloth, and it is a big problem that a printed image with good sharpness cannot be obtained. As a measure to improve the problem, the cloth is previously treated with a compound selected from the group of water-soluble polymers, water-soluble salts, and water-insoluble inorganic fine particles, which are substantially non-dyeing to the dye used. , A method of performing ink jet dyeing (Japanese Patent Publication No. 63-3
1594).

[0003]

Dyes and dyeing conditions suitable for the types of fibers used for dyeing fabrics must be finely adjusted. However, according to the above-mentioned conventional techniques, sharpness and build-up property are good in inkjet dyeing of various fibers, reproducibility is good, and dyeing is very difficult. The present invention solves these problems and provides a cloth for inkjet dyeing, which can be dyed with good sharpness, good build-up property and good reproducibility.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors to achieve these objects, the use of a water-insoluble water-absorbent resin enables dyeing improved as described above. The present invention has been discovered and the present invention has been reached. That is, the present invention has a water absorption capacity of 50 to 1,000 m for pure water.
The water-insoluble water-absorbent resin of 1 / g is 0.01 to the cloth.
10% by weight of the cloth for inkjet dyeing (first invention); and 0.01 to 10% by weight of the water-insoluble water-absorbent resin to the cloth, and then a dye by an inkjet method An inkjet dyeing method for fabrics (second invention), which comprises applying an ink and then heat-fixing and then dyeing and removing the water-insoluble water-absorbent resin.

In the present invention, examples of the water-insoluble water-absorbent resin include starch or cellulose (a),
A monomer selected from a water-soluble monomer having a carboxyl group or a sulfonic acid group and a water-soluble monomer by hydrolysis (hereinafter referred to as a water-soluble monomer) (b),
A water-insoluble water-absorbent resin (hereinafter referred to as a starch or a cellulose-based crosslinked product) obtained by polymerizing the crosslinking agent (c) as an essential component and performing hydrolysis as required.

Details of (a), (b), and (c) used in the production of the water-insoluble water-absorbent resin exemplified above,
The ratios of (a), (b), and (c), the production method, and specific examples of the water-insoluble water absorbent resin are described in JP-A-52-25886.
No. 53, Japanese Patent Publication No. 53-46199, Japanese Patent Publication No. 53-4620
No. 0 and Japanese Patent Publication No. 55-21041.

Water-insoluble water-absorbent resins other than those exemplified above include, for example, those obtained by polymerizing (a) and (b) (hydrolyzate of starch-acrylonitrile graft polymer, cellulose-acrylonitrile graft polymer). A hydrolyzate of the combined product, etc., hereinafter referred to as starch or cellulose-acrylonitrile-grafted polymer); a crosslinked product of (a) (crosslinked product of carboxymethyl cellulose);
Copolymer of (b) and (c) (partial hydrolyzate of crosslinked polyacrylamide, crosslinked acrylic acid-acrylamide copolymer, crosslinked sulfonated polystyrene, JP-A-52-14689 and JP-A-52-14689) Sho 52-27455
Vinyl ester-unsaturated carboxylic acid copolymer saponified product, crosslinked polyacrylic acid salt, crosslinked acrylic acid-acrylic ester acid copolymer, crosslinked isobutylene-maleic anhydride copolymer, And a crosslinked carboxylic acid-modified polyvinyl alcohol); and a polymer (b) having self-crosslinking property (self-crosslinking polyacrylic acid salt, etc.). Further, two or more kinds of the water-insoluble water-absorbent resins exemplified above may be used in combination.

Among these, preferred ones are; and among those exemplified as, a partial hydrolyzate of crosslinked polyacrylamide, a crosslinked acrylic acid-acrylamide copolymer, a crosslinked polyacrylic acid salt, and a crosslinked polyacrylic acid salt. Acrylic acid-acrylic ester acid copolymers, crosslinked isobutylene-maleic anhydride copolymers, and crosslinked carboxylic acid-modified polyvinyl alcohols.

The water absorption capacity of the water-insoluble water-absorbent resin (A) for pure water is usually 50 to 1,000 ml / g, preferably 100 to 1,000 ml / g. The shape of the water-insoluble water-absorbent resin is not particularly limited, but powdery or granular (particle size is usually 5 mm or less) is preferable.

The ink jet system adopted in the present invention can be used as long as the dye ink is effectively separated from the nozzle and applied to the cloth as the range,
A typical method thereof is, for example, 1EEE Transcushion Industry Applications, Vol.
1A-13, No. 1 (February 3, 1977) Electronics, April 19, 1976, etc.

Typical methods are as follows (1)-
There is a method of (3). That is, (1) electrostatic attraction method; strong electrolysis is applied between the nozzle and an accelerating electrode placed a few mm in front of the nozzle, and the ink is made into particles from the nozzle and drawn out one after another, and the drawn ink particles are deflected electrodes. An information signal is given to the deflection electrode for recording when flying between.

(2) Ultrasonic vibration type: A small pump applies a high pressure to ink and mechanically vibrates the nozzle with a crystal oscillator or the like to forcibly eject fine ink particles.
The ejected ink particles are charged according to the information signal at the same time as the ejection. When the charged ink particles pass between the deflection electrode plates, they are deflected according to the charge amount.

(3) Piezo element system: A method using a piezo element, in which an electric signal is applied to the piezo element to cause mechanical displacement, thereby applying pressure to ink and ejecting it from a nozzle.

These various ink jet systems can be appropriately selected and adopted in the present invention.

The cloth in the present invention may be woven, knitted or non-woven, and the fiber material used for the cloth is
Any synthetic fiber (polyester, polyamide, acrylic fiber, etc.), semi-synthetic fiber (acetate, rayon, etc.), natural fiber (cotton, silk, wool, etc.), and a mixture of these (blend product, twisted product, knitted woven product) ) And all other fiber materials can be applied.

The dye ink in the present invention is required to contain a dye capable of being dyed to a cloth, and this dye includes an acid dye, a direct dye, a reactive dye, a cationic dye, a disperse dye and the like. can give.

The dye constituting the dye ink must be changed according to the fiber material used. For example,
When the fiber material constituting the cloth is polyester or acetate fiber, the dye ink is composed of disperse dye.

When the material constituting the cloth is a material capable of dyeing anionic dyes such as wool, silk, polyamide, cotton and rayon, an anionic dye such as a direct dye, an acid dye or a reactive dye is applied as the dye. Further, in the case of a cationic dyeable material such as acrylic fiber or cationic dyeable polyester fiber, a cationic dye is applied as the dye.

The disperse dyes include azo type, anthraquinone type, nitrodiphenylamine type, naphthalimide type,
Examples include naphthoquinone imide type and methine type. Specifically, New Edition Dye Handbook (Publisher: Maruzen Co., Ltd.) No. 72
Examples thereof include dyes described on pages 5 to 816.

Examples of the direct dye include azo type, stilbene type, thiazole type, dioxazine type and phthalocyanine type dyes. Specifically, the same dye handbook 317-3
Examples thereof include dyes described on page 96.

Examples of the acid dye include azo type, anthraquinone type, triphenylmethane type, xanthine type and the like. Specific examples thereof include the dyes described on pages 393 to 526 of the same dye manual.

Examples of reactive dyes include azo, anthraquinone and phthalocyanine dyes. Specific examples thereof include the dyes described on pages 881 to 934 of the same dye manual.

Specific examples of the cationic dye include the dyes described on pages 529 to 562 of the same dye manual.

The dye ink may have an ink design suitable for each ink jet system, but a water-based ink is preferably applied from the viewpoint of environmental and fabric bleeding.

If necessary, the ink may have physical property modifiers (viscosity, surface tension, conductivity, pH, etc.), antifungal agents,
Additives such as a bactericidal agent, a chelating agent, and an ink drying inhibitor are added. The ink drying inhibitor has a function of preventing ink clogging of an inkjet nozzle, and is, for example, polyhydric alcohol such as ethylene glycol and glycerin, N-alkylpyrrolidone such as N-methylpyrrolidone and N-ethylpyrrolidone, methylcellosolve, and ethylcellosolve. , Ether compounds such as methyl carbitol, formamide derivatives such as N-cyclohexylformamide and N-, N-dibutylformamide, and aralkyl alcohols such as benzyl alcohol and 1-phenylethyl alcohol.

As an example of the method for attaching the water-insoluble water-absorbent resin to the cloth, first, water or a hydrophilic organic solvent (methanol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethylformamide, etc.) or water and a hydrophilic organic solvent are used. The water-insoluble water-absorbent resin is dispersed in the mixed solution of to prepare a dispersion solution. The fabric is then treated with this dispersion by any method such as padding, spraying, coating and printing and dried. If it is equipped with an anti-exposure device, a dispersion solution may be prepared and used with an aromatic solvent (toluene, xylene, etc.).

The amount of the water-insoluble water-absorbent resin attached is 0.01 to 10% by weight, preferably 0.1 to 5% by weight of the cloth.
% By weight. If it is less than 0.01%, the dye ink has a small bleeding preventive property, and a printed image with good sharpness cannot be obtained. Further, if it exceeds 10% by weight, the bleeding prevention property is increased, but the build-up property of the printed image is extremely deteriorated, which is not preferable.

As a specific example of the inkjet dyeing method of the present invention, first, a dispersion solution of the water-insoluble water-absorbent resin is applied to the cloth and dried to obtain the inkjet dyeing cloth of the present invention. Dye ink is printed on this dyeing cloth with an inkjet dyeing machine. Next, the dye applied to the cloth is subjected to steaming or dry heat treatment in order to heat and develop the color. The heat-fixing conditions vary depending on the type of dye used and the type of cloth used, but in the case of steaming, 1 to 100-130 ° C
It is 0 to 30 minutes, and in the case of dry heat, it is processed at 180 to 210 ° C. for 1 to 5 minutes. Finally, soaping or reduction cleaning is performed to remove the undyed dye and the water-insoluble water-absorbent resin.

In the present invention, when the dye ink is applied (printed) to the cloth to which the water-insoluble water-absorbent resin is adhered by the ink jet method, the sharpness and the build-up property are good, and the dyeing can be performed with good reproducibility. I will consider whether or not.

In print dyeing, in order to improve the sharpness and build-up property, it depends on how much and sharply the dye is placed on the fabric so that migration of the dye does not occur during heat fixing. By the way, as described above, the ink-jet type dye ink is a water-based medium and is an aqueous solution of a water-soluble dye or an aqueous dispersion of a finely dispersed dye, and the ink can be dyed quickly regardless of the amount of the ink. The point is to make the body absorb it.

When ink adheres to the dyeing fabric of the present invention, a large amount of ink absorbs speedily without bleeding. It is considered that this is because the ink is trapped in the crosslinked polymer network of the water-insoluble water-absorbent resin to prevent migration and form sharp prints. Further, since the water-insoluble water-absorbent resin has a poor affinity with each dye, the dye trapped in the polymer network does not diffuse inside the water-insoluble water-absorbent resin even when heat-fixed, and has a good affinity. Migrate only to fine fiber parts.

On the other hand, in the prior art method using a water-soluble polymer or water-soluble salt, when ink is similarly deposited,
The ink dissolves these compounds and absorbs the ink while spreading, so-called bleeding. Further, in the conventional method using water-insoluble inorganic fine particles, the ink is contained in the gaps between the particles by a capillary phenomenon to take an absorbing state. However, since it is insoluble in water, the absorption rate is slow and the absorption amount is limited.

The dye ink is applied (printed) to the dyeing cloth of the present invention to which the water-insoluble water-absorbing resin is adhered by an ink jet method, which is a water-soluble polymer, water-soluble salt or water-insoluble inorganic fine particles of the prior art. This is the reason why the sharpness and build-up property are superior to those obtained by using the compound selected from the group (1).

[0034]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following,% means% by weight.

1. Diffusivity: In inkjet dyeing,
It is the ratio of the dot diameter on the cloth to the diameter of the ink droplet in flight. The smaller the number, the less ink bleeding. 2. Sharpness: A geometric pattern was printed and dyed by inkjet dyeing, and the sharpness was visually judged. (Judgment Criteria) ⊚: Printed and dyed without fine bleeding and fine pattern fine lines are clear. ◯: Printed and dyed without bleeding and the pattern is decent. Δ: Printed and dyed with slight blurring and the fine lines of the pattern are unclear. X: Printed and dyed with bleeding and fine pattern lines cannot be expressed. 3. Saturation amount: In inkjet dyeing, solid printing and dyeing were performed, the saturation amount (* C) was measured, and the saturation difference (Δ * C) was calculated. Saturation difference here means that treated with a treatment agent,
It is the difference in color saturation of each dyed cloth without the treatment agent. The smaller the value, the smaller the difference in saturation. 4. Build-up property; 3. The lightness (L value) of the dyed cloth is M
The color intensity was measured by measuring the color with an ulti Spectro MSC-2 [manufactured by Suga Test Instruments Co., Ltd.]. The smaller the value, the deeper the dyeing.

Example 1 Starch cross-linking water absorbent resin, Sunwet 1M-10
A 1% dispersion solution of 00MPS (manufactured by Sanyo Kasei Co., Ltd.) was prepared, and the polyester processed fabric was padded (drawing ratio 5
0%) and dried at 100 ° C. for 2 minutes to prepare a fabric for inkjet dyeing. The cloth was subjected to inkjet dyeing under the following conditions.

(Composition of Inkjet Ink) Sumikaron Brilliant Blue S-BL 8 (part) [Disperse Dye, Sumitomo Chemical Co., Ltd.] N-Methylpyrrolidone 10 Ethylene Glycol 15 Ion-exchanged Water 67 ---------- −−−−−−−−−−−−−−−−−−−−−−−−−− Total 100 Viscosity (cps / 25 ° C.): 8 Surface tension (dyne / cm, 25 ° C.): 58 2.2 Specific conductivity (mμ, 25 ° C.): 3.3 pH: 7.8

(Inkjet dyeing) (1) Printing 1) Inkjet method: On-demand method 2) Nozzle diameter: 60μ 3) Applied voltage: 50V (2) Color development (heat treatment, reduction cleaning) 1) Heat treatment: 180 ° C x 2 minutes , Fixing treatment 2) Reduction cleaning: Hydrosulfite 1 (g / l) NaOH 1 Ionette RK-15 1 [manufactured by Sanyo Kasei Co., Ltd.] 80 ° C x 20 minutes treatment, water washing, drying

Example 2 A crosslinked polyacrylic acid (salt) type water absorbent resin [Aquaric CA-ML manufactured by Nippon Shokubai Kagaku Co., Ltd.] was used instead of the starch type crosslinked water absorbent resin of Example 1. A fabric for inkjet dyeing was prepared. The same inkjet dyeing test as in Example 1 was performed.

Example 3 Ink jet using a crosslinked polyacrylic acid (salt) type water absorbent resin [manufactured by Sanyo Kasei Co., Ltd., Sunwet 1M-5000] instead of the starch type crosslinked water absorbent resin of Example 1. A dyeing fabric was prepared.

Comparative Examples 1 and 2 Instead of the starch-based crosslinkable water absorbent resin of Example 1, gum arabic (Comparative Example 1) and montmorillonite (Comparative Example 2)
A 1% aqueous solution of each of the above was used to prepare a cloth for inkjet dyeing. Then, the same inkjet dyeing test as in Example 1 was performed.

The diffusivity of the ink-jet dyeing fabrics of Examples 1 to 3 and Comparative Examples 1 and 2, and the sharpness, the amount of saturation (* C) and the build-up property (L value) of each of the dyed fabrics were measured. The results are shown in Table 1 below.

[0043]

[Table 1]

From the evaluation results shown in Table 1 above, the inkjet dyed fabric of the present invention was excellent in diffusivity and sharpness, and an inkjet image having good saturation and build-up property was obtained. On the other hand, Comparative Examples 1 and 2 were poor in diffusivity and sharpness as compared with the fabric of the present invention, and were also inferior in saturation and build-up property.

Example 4 Starch cross-linking type water absorbent resin, Sunwet 1M-10
A 1% dispersion solution of 00MPS [manufactured by Sanyo Kasei Co., Ltd.] was prepared. Padding cotton broad # 80 (drawing ratio 80
%) And dried at 105 ° C. for 2 minutes to prepare a fabric for inkjet dyeing. The cloth was subjected to inkjet dyeing under the following conditions.

(Composition of Inkjet Ink) Kaya-on Scarlet P-RN [Reactive Dye, Nippon Kayaku Co., Ltd.] 10 (parts) Urea 10 Sodium carbonate 2 Glycerin 15 Ion-exchanged water 63 ---------- −−−−−−−−−−−−−−−−−−−−−−−− Total 100 Viscosity (cps / 25 ° C.): 10 Surface tension (dyne / cm, 25 ° C.): 55.3 Specific conductivity (mμ, 25 ° C): 2.4 pH: 10.2

(Inkjet dyeing) (1) Printing 1) Inkjet method: On-demand method 2) Nozzle diameter: 60μ 3) Applied voltage: 50V (2) Color development (superheated steam treatment, reduction cleaning) 1) Superheated steam treatment: 130 C. × 3 minutes treatment 2) Soaping: Granup QF-105K 1 (g / l) [manufactured by Sanyo Kasei Co., Ltd.] 80 ° C. × 20 minutes treatment, water washing, drying

Example 5 A cloth for inkjet dyeing was prepared by using a crosslinked isobutylene-maleic anhydride copolymer water-absorbent resin [KI gel 201K, Kuraray Co., Ltd.] instead of the starch-based crosslinkable water-absorbent resin of Example 4. Created. The same inkjet dyeing test as in Example 4 was performed.

Example 6 A cloth for ink jet dyeing was prepared by using a crosslinked carboxylic acid-modified polyvinyl alcohol-based water absorbent resin [Igetagel P, manufactured by Sumitomo Chemical Co., Ltd.] instead of the starch-based crosslinked water absorbent resin of Example 4. It was created. The same inkjet dyeing test as in Example 4 was performed.

Comparative Examples 3 and 4 Polyvinyl alcohol [PVA117, Comparative Example 3], CaC instead of the starch-based cross-linking type water absorbent resin of Example 4
A 1% aqueous solution of each of l ₂ (Comparative Example 4) was used to prepare a cloth for inkjet dyeing. Then, the same inkjet dyeing test as in Example 4 was performed.

The diffusivity of the ink-jet dyeing fabrics of Examples 4 to 6 and Comparative Examples 3 and 4, and the sharpness, the amount of saturation (* C) and the build-up property (L value) of each of the dyed fabrics were measured. The results are shown in Table 2 below.

[0052]

[Table 2]

From the evaluation results shown in Table 2 above, the inkjet dyed fabrics of the present invention (Examples 4 to 6) were excellent in diffusivity, sharpness, and good in saturation and build-up property. In contrast, Comparative Examples 3 and 4 were slightly inferior in diffusivity and sharpness to the fabric of the present invention, and were also inferior in saturation and build-up property.

[0054]

By using the ink-jet dyeing fabric of the present invention, the sharpness and build-up property are good,
Can be dyed with good reproducibility. Therefore, according to the dyeing method of the present invention, it is possible to obtain a valuable printed product similar to the conventional high-quality printed products such as roller printing and screen printing.

Claims (2)

[Claims] 1. A water absorption capacity for pure water of 50 to 1,000.
0.01 ml / g of water-insoluble water-absorbent resin is applied to the fabric.
A cloth for inkjet dyeing, characterized in that the cloth is adhered by 10% by weight. 2. The water-insoluble water-absorbent resin is applied to a cloth in an amount of 0.01 to 10% by weight, a dye ink is applied by an inkjet method, and then heat-fixing treatment is performed, and then the water-insoluble water-absorbent resin is applied. A method for ink-jet dyeing a cloth, comprising: