JP2841019B2 - Inkjet dyeing carpet substrate and dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carpet base material and a method for dyeing a carpet base material capable of obtaining a printed image having excellent sharpness and build-up properties by applying a dye ink by an ink jet system.

[0002]

2. Description of the Related Art When a pattern is dyed on a carpet substrate by an ink jet method, "bleeding" of a dye ink occurs, and a printed image having good sharpness cannot be obtained.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and provides an ink-jet dyeing carpet substrate which has excellent sharpness and build-up property, and can be dyed clearly with good reproducibility.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve this object, and as a result, the dyeing improved as described above by previously attaching a water-insoluble water-absorbing resin to a carpet base material. Have been found to be possible, and the present invention has been reached. That is, the present invention is characterized in that a water-insoluble water-absorbent resin having a water absorption capacity for pure water of 50 to 1,000 ml / g is adhered to a carpet substrate with a pile in an amount of 0.01 to 10% by weight. The water-insoluble water-absorbent resin is added to the carpet substrate for dyeing (first invention);
A second ink jet dyeing method for carpet substrates, comprising applying a dye ink by an ink jet method after adhering the dye by weight, followed by heat fixing treatment.

[0005] The water-insoluble water-absorbing resin used in the present invention includes, for example, starch or cellulose (a), a water-soluble monomer having a carboxyl group or a sulfonic acid group, and a water-soluble monomer which becomes water-soluble by hydrolysis. Monomer selected from monomers (hereinafter referred to as water-soluble monomer)
(B) and a crosslinking agent (c) are polymerized as essential components,
A water-insoluble water-absorbent resin (hereinafter, referred to as a starch or a cellulose-based crosslinked product) obtained by performing hydrolysis as necessary is mentioned.

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

Examples of the water-insoluble water-absorbing resin 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 or the like, hereinafter referred to as starch or a cellulose-acrylonitrile graft polymer); a crosslinked product of (a) (a crosslinked product of carboxymethylcellulose);
Copolymers of (b) and (c) (partially hydrolyzed cross-linked polyacrylamide, cross-linked acrylic acid-acrylamide copolymer, cross-linked sulfonated polystyrene, JP-A-52-14689 and JP-A-52-14689) 1975-27455
JP-A-58-133, saponified vinyl ester-unsaturated carboxylic acid copolymer, cross-linked polyacrylate, cross-linked acrylic acid-acrylate copolymer, cross-linked isobutylene-maleic anhydride copolymer, And a crosslinked carboxylic acid-modified polyvinyl alcohol); and a polymer (b) having self-crosslinking properties (such as a self-crosslinkable polyacrylate). The water-insoluble water-absorbing resins exemplified above may be used in combination of two or more.

[0008] Of these, preferred are; and those exemplified as: and partially hydrolyzed cross-linked polyacrylamide, cross-linked acrylic acid-acrylamide copolymer, cross-linked polyacrylate, cross-linked polyacrylate, An acrylic acid-acrylate copolymer, a cross-linked isobutylene-maleic anhydride copolymer, and a cross-linked carboxylic acid-modified polyvinyl alcohol.
The water absorbing ability of the water-insoluble water-absorbent resin (A) with respect to pure water is as follows:
Usually 50 to 1,000 ml / g, preferably 100 to
It is 1,000 ml / g. The shape of the water-insoluble water-absorbent resin is not particularly limited, but is preferably powdery or granular (the particle size is usually 5 mm or less).

The ink jet system employed in the present invention can be used as long as the dye ink is effectively separated from the nozzles and applied to the carpet base material as the projectile. For example, IEEE Transcushioning Industry Applications, V
ol. 1A-13, No. 1 (February 3, 1977) Electronics, April 19, 1976, and the like.

As a typical method, there is (1) an electrostatic suction method, in which a strong electric field is applied between a nozzle and an accelerating electrode placed several mm in front of the nozzle to cause ink to be ejected from the nozzle. Then, when the extracted ink particles fly between the deflecting electrodes, an information signal is applied to the deflecting electrodes for recording. (2) There is an ultrasonic vibration type. In this method, a high pressure is applied to the ink by a small pump, and the nozzle is mechanically vibrated by a quartz oscillator or the like, thereby forcibly ejecting 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 amount of charge. (3) There is a piezo element system, which uses a piezo element, and applies an electric signal 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 employed in the present invention.

The carpet substrate in the present invention includes:
Arbitrary synthetic fibers (polyester, polyamide, acrylic fiber, etc.), semi-synthetic fibers (acetate, rayon, etc.), natural fibers (cotton, silk, wool, etc.), and mixtures of these (blended, twisted, cross-woven) ), Etc., manufactured from all fiber materials.
[I] Pile (yarn or fiber protruding from the base cloth) and a carpet base material described in “June 15, 1979, issued by Toyo Keizai Shinposha”.

Specific examples of [I] include a woven carpet (1), a knitted carpet (2), a tufted carpet (3), a stitched-on pile carpet (4), a bonded pile carpet (5), and a flocked carpet. (6) and a base material such as a knotted pile carpet (7). Among these [I], the tufted carpet substrate (3) is preferable. Further, interior base materials (wall hangings, curtains, cushions, decorations, etc.) having the same structure as the carpet other than the carpet base materials are also included in the technical scope of the present invention.

The dye ink used in the present invention needs to contain a dye capable of dyeing a carpet substrate. Examples of the dye include acid dyes, direct dyes, reactive dyes, cationic dyes, and disperse dyes. And so on.

The dye constituting the dye ink must be changed according to the fiber material used. For example,
The fiber material constituting the carpet base material is polyester,
In the case of acetate fibers, the dye ink is formed using a disperse dye. When the material constituting the carpet substrate is a material that can be dyed with an anionic dye such as wool, silk, polyamide, cotton, or rayon, an anionic dye such as a direct dye, an acid dye, or a reactive dye is used as the dye. In the case of a material dyeable with a cationic dye such as an acrylic fiber or a cationic dyeable polyester fiber, a cationic dye is used as the dye.

As disperse dyes, azo dyes, anthraquinone dyes, nitrodiphenylamine dyes, naphthalimide dyes,
Examples include naphthoquinone imides and methines. Specifically, New Edition Dye Handbook (Issued by Maruzen Co., Ltd.) No. 72
And dyes described on pages 5 to 816. Examples of the direct dye include an azo type, a stilbene type, a thiazole type, a dioxazine type and a phthalocyanine type. Specific examples include the dyes described in the Handbook of Dyes, pages 317 to 396. Examples of the acid dye include an azo type, an anthraquinone type, a triphenylmethane type and a xanthine type.
Specific examples include the dyes described in the Handbook of Dyes, pp. 393-526. Examples of reactive dyes include azo, anthraquinone, and phthalocyanine dyes. Specific examples include the dyes described in the Handbook of Dyes, pages 881 to 934. Specific examples of the cationic dye include the dyes described in the Handbook of Dyes, pp. 529-562.

The dye ink may be designed so as to be suitable for each ink jet system. However, a water-based ink is preferably applied from the viewpoint of environmental and bleeding on a carpet substrate.

If necessary, a physical property modifier (adjustment of viscosity, surface tension, electric conductivity, pH, etc.), a fungicide,
Additives such as a bactericide, a chelating agent, and an ink drying inhibitor are blended. The ink drying inhibitor has a function of preventing ink clogging of the ink jet nozzle. For example, polyhydric alcohols such as ethylene glycol and glycerin, N-alkylpyrrolidone such as N-methylpyrrolidone and N-ethylpyrrolidone, methylcellosolve, and ethylcellosolve And ether compounds such as methylcarbitol, formamide derivatives such as N-cyclohexylformamide and N-, N-dibutylformamide, and aralkyl alcohols such as benzyl alcohol and 1-phenylethyl alcohol.

Examples of the method of attaching the water-insoluble water-absorbent resin to a carpet substrate include: a hydrophilic organic solvent (methanol, isopropyl alcohol, ethylene glycol, propylene glycol, dimethylformamide, etc.) or water and a hydrophilic organic solvent; The water-insoluble water-absorbent resin is dispersed in a mixed solvent of the above to prepare a dispersion. Next, the carpet substrate is treated with this dispersion by any method such as a pad method, a spray method, a coating method and a printing method, and dried. If an anti-exposure device is provided, a dispersion may be prepared from an aromatic solvent (toluene, xylene, etc.) and used. A preferred treatment method is a spray method.

The amount of the water-insoluble water-absorbing resin adhered is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the carpet base materials. If it is less than 0.01%, the bleeding preventing property of the dye ink is small, and a print image with good sharpness cannot be obtained. On the other hand, when the content exceeds 10% by weight, the bleeding prevention property is increased, but the build-up property of a printed image is extremely lowered, which is not preferable.

As a specific example of the ink jet dyeing method of the present invention, first, a dispersion comprising the water-insoluble water-absorbent resin is applied to a carpet base material and dried to obtain the ink jet dyeing carpet base material of the present invention. A dye ink is printed on the dyeing carpet substrate by an ink jet dyeing machine. Next, steam or dry heat treatment is performed to heat and color the dye applied to the carpet base material. The heat fixing conditions vary depending on the type of dye and the type of carpet base material used, but in the case of steaming, the temperature is set to 10 to 3 at 100 to 130 ° C.
In the case of 0 minutes and dry heat, the treatment is performed at 180 to 210 ° C. for 1 to 5 minutes. After the heat fixing treatment, the undyed dye and the water-insoluble water-absorbent resin may be removed by washing, or may not be removed by washing. When washing and removing the undyed dye and the water-insoluble water-absorbent resin, soaping is necessary,
Perform reduction cleaning, post-treatment, etc.

In the present invention, when the dye ink is applied (printed) to the carpet substrate to which the water-insoluble water-absorbent resin is adhered by the ink jet method, the sharpness, the build-up property are good, and the reproducibility is good. Consider whether it can be dyed. In order to improve the sharpness and the build-up property in print dyeing, it depends on how much the dye is applied on the carpet base material, how much the dye is applied, and whether or not migration of the dye occurs during heat fixing. . By the way, as described above, the dye-based ink of the ink jet system is a water-based medium and an aqueous solution of a water-soluble dye or a water dispersion of a finely dispersed dye,
The point is how quickly the ink is absorbed by the to-be-coated body regardless of the amount of the ink.

When the ink adheres to the dyeing carpet substrate of the present invention, a large amount of ink is absorbed quickly without bleeding, and a sharp print is formed. This is because the ink is confined within the crosslinked polymer network of the water-insoluble water-absorbent resin and does not migrate.
Further, even in the subsequent heat fixing treatment, the water-soluble dye does not diffuse in the polymer network due to poor affinity with the water-insoluble water-absorbent resin, and migrates only to the fiber portion having good affinity. , Sharp print is fixed. The dyeing carpet base material of the present invention is excellent in sharpness and build-up property due to the above-mentioned action.

[0023]

The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the following,% indicates% by weight, and the performance evaluation is as follows. 1. Sharpness: A geometric pattern was printed and dyed by inkjet dyeing, and the sharpness was visually judged. (Judgment Criteria) A: Printed and dyed without any bleeding, and fine lines of the pattern are clear. ：: Printed and dyed without bleeding, and the pattern was acceptable. Δ: Slightly blurred, printed and dyed, and fine lines of the pattern were unclear. ×: Printed and stained with bleeding, and the fine lines of the pattern could not be expressed. 2. Saturation difference: Solid printing and dyeing in inkjet dyeing, measuring the amount of saturation (C *) with Multi SpectroMSC-2 [manufactured by Suga Test Instruments Co., Ltd.]
*) Was calculated. The term “saturation difference” as used herein refers to a difference in saturation between a stained sample that has been treated with a treatment agent and that that has not been treated with a treatment agent. 3. Build-up property 2. The lightness (L value) of the stained carpet of Multi S
Spectro MSC-2 [manufactured by Suga Test Instruments Co., Ltd.] was used to measure the color, and the color density was measured. The smaller the value, the deeper the dye.

Example 1 Crosslinked starch-based water-absorbing resin, Sunwet IM-10
A 1% dispersion of 00MPS [manufactured by Sanyo Chemical Co., Ltd.] [a mixed solvent of water / ethylene glycol = 7/3 (weight ratio)] is applied to a polyester cut pile tufting carpet substrate by a spray method, and then an infrared lamp is applied. To prepare a carpet substrate for inkjet dyeing (the amount of the water-absorbing resin adhered was 0.3%). The carpet substrate was subjected to inkjet dyeing under the following conditions. (Composition of Inkjet Ink) Sumicaron Brilliant Blue S-BL 8 (parts) [Disperse Dye, Sumitomo Chemical Co., Ltd.] N-Methylpyrrolidone 10 Ethylene glycol 15 Ion-exchanged water 67 -------------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 100

(Properties of ink) Viscosity (cps / 25 ° C.): 8 Surface tension (dyne / cm, 25 ° C.): 58.2 PH: 7.8

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

Example 2 A crosslinked polyacrylic acid (salt) -based water-absorbing resin [Aqualic CA-ML, manufactured by Nippon Shokubai Kagaku Co., Ltd.] was used instead of the starch-based cross-linked water-absorbing resin of Example 1. Then, a carpet substrate for inkjet dyeing (the amount of the water-absorbing resin attached was 0.3%) was prepared. Next, the same inkjet dyeing test as in Example 1 was performed.

Example 3 Instead of the starch-based crosslinked type water-absorbing resin of Example 1, a crosslinked polyacrylic acid (salt) -based water-absorbing resin [Sunwet IM-5000, manufactured by Sanyo Chemical Co., Ltd.] was used for ink-jetting. A carpet substrate for dyeing (the amount of the water-absorbing resin attached was 0.3%) was prepared. Next, the same inkjet dyeing test as in Example 1 was performed.

Comparative Example 1 The same ink-jet dyeing test as in Example 1 was performed without using the water-absorbing resin.

With respect to the ink-jet dyeing carpet base materials of Examples 1 to 3 and Comparative Example 1, sharpness and chroma difference (ΔC
*) And build-up properties (L values) were measured, and the results are shown in Table 1.

[0031]

[Table 1]

From the evaluation results shown in Table 1, it can be seen that the ink-jet dyed carpet substrate of the present invention can provide an ink-jet image having excellent sharpness and good chroma and build-up properties.

Example 4 Crosslinked starch-based water-absorbing resin, Sunwet IM-10
A 1% dispersion of 00MPS [manufactured by Sanyo Chemical Co., Ltd.] [a mixed solvent of water / ethylene glycol = 7/3 (weight ratio)] is applied to a nylon cut pile tufting carpet substrate by a spray method and then heated at 105 ° C. Dry, carpet base material for inkjet dyeing (adhesion amount of water absorbent resin is 0.3%)
It was created. The carpet substrate was subjected to an inkjet dyeing test under the following conditions.

(Composition of Inkjet Ink) Suminol Milling Red RS 10 (part) [Acid Dye, Sumitomo Chemical Co., Ltd.] Thiourea 8 Ethylene glycol 5 Ion-exchanged water 77 −−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−− Total 100

(Properties of ink) Viscosity (cps / 25 ° C.): 7 Surface tension (dyne / cm, 25 ° C.): 56.9 PH: 6.4

(Inkjet dyeing) (1) Printing 1) Inkjet method: On-demand method 2) Nozzle diameter: 60μ 3) Applied voltage: 50V (2) Color development (steaming) 1) Superheated steam treatment: 102 ° C to 103 ° C × 3
0 minute treatment (3) Drying 1) Drying: Drying with infrared lamp

Example 5 A carpet for ink jet dyeing using a crosslinked isobutylene maleic anhydride copolymer water absorbent resin [Kuraray Co., Ltd., KI gel 201K] instead of the starch-based crosslinked type water absorbent resin of Example 4. A substrate (the amount of the water-absorbing resin attached was 0.3%) was prepared. The same inkjet dyeing test as in Example 4 was performed.

Example 6 An ink-jet dyeing carpet using a crosslinked carboxylic acid-modified polyvinyl alcohol-based water-absorbent resin [manufactured by Sumitomo Chemical Co., Ltd., Igetagel P] instead of the starch-based crosslinkable water-absorbent resin of Example 4. A substrate (the amount of the water-absorbing resin attached was 0.3%) was prepared. The same inkjet dyeing test as in Example 4 was performed.

Comparative Example 2 The same ink-jet dyeing test as in Example 4 was performed without using the water-absorbing resin.

For the ink-jet dyeing carpet base materials of Examples 4 to 6 and Comparative Example 2, sharpness and chroma difference (ΔC
*) And build-up properties (L values) were measured, and the results are shown in Table 2.

[0041]

[Table 2]

From the evaluation results shown in Table 2, it can be seen that the ink-jet dyed carpet base material of the present invention (Examples 4 to 6) is excellent in sharpness and can obtain an ink-jet image with good chroma and build-up properties.

Example 7 Crosslinked starch-based water-absorbing resin, Sunwet IM-10
After applying a 20% dispersion [ethylene glycol dispersion] of 00SP [manufactured by Sanyo Chemical Co., Ltd.] to a polyester cut pile tufting carpet substrate by a spray method,
After drying at 5 ° C., an ink-jet dyeing carpet substrate (the amount of the water-absorbing resin attached was 5%) was prepared. The carpet substrate was subjected to an inkjet dyeing test under the following conditions. (Composition of inkjet ink) Kayalon polyester 10 (part) Scarlet RL-SF [Disperse dye, Nippon Kayaku (manufactured)] N-methylpyrrolidone 15 glycerin 5 ethylene glycol 15 ion-exchanged water 55 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Total 100

(Properties of ink) Viscosity (cps / 25 ° C.): 10 Surface tension (dyne / cm, 25 ° C.): 50.3 PH: 7.2

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

Example 8 The same 2.5% dispersion of a water-absorbent resin [water / ethylene glycol = 5/5 (weight ratio) mixed solvent] as in Example 7 was applied to a polyester cut pile tufting carpet substrate. After coating by a spray method, drying at 105 ° C. and drying the ink-jet dyeing carpet substrate (the amount of the water-absorbing resin is 5
%)made. An ink jet dyeing test was performed on the carpet substrate in the same manner as in Example 7.

Comparative Example 3 The same ink-jet dyeing test as in Example 7 was performed without using the water-absorbing resin.

For the ink-jet dyeing carpet substrates of Examples 7 and 8 and Comparative Example 3, the sharpness and the saturation difference (ΔC
*) And build-up property (L value) were measured, and the results are shown in Table 3.

[0049]

[Table 3]

From the evaluation results shown in Table 3, it can be seen that the ink-jet dyed carpet base materials of the present invention (Examples 7 and 8) are excellent in sharpness, and can obtain an ink-jet image with good chroma and build-up properties.

Example 9 The dispersion of Example 7 was applied to a nylon cut pile tufting carpet substrate by a spray method, and then dried at 105 ° C. to obtain a carpet substrate for inkjet dyeing (the amount of the water-absorbing resin adhered was 3%). )made. The carpet substrate was subjected to an inkjet dyeing test under the following conditions. (Composition of Inkjet Ink) Nirosan Navy P-RBL 12 (parts) [Acid Dye, Sando Co., Ltd.] Glycerin 5 Ethylene glycol 15 Urea 5 Ion-exchanged water 63------------ −−−−−−−−−−−−−−−−−−−−−−−−−−− Total 100

(Properties of ink) Viscosity (cps / 25 ° C.): 13 Surface tension (dyne / cm, 25 ° C.): 52.6 PH: 7.2

(Inkjet dyeing) (1) Printing 1) Inkjet method: On-demand method 2) Nozzle diameter: 60μ 3) Applied voltage: 50V (2) Color development (steaming) 1) Superheated steam treatment: 102 ° C to 103 ° C × 3
0 minute treatment (3) Rinse with water: normal temperature water (4) Dehydration: Mangle dehydration (5) Drying: 105 ° C x 30 minutes

Example 10 The dispersion of Example 8 was applied to a nylon pile tufting carpet substrate by a spray method, and then dried at 105 ° C. to obtain a carpet substrate for inkjet dyeing (the amount of the water-absorbing resin adhered was 3%). It was created. An ink jet dyeing test was performed on the carpet substrate in the same manner as in Example 9.

Comparative Example 4 The same ink-jet dyeing test as in Example 9 was performed without using the water-absorbing resin.

For the ink-jet dyeing carpet base materials of Examples 9 and 10 and Comparative Example 4, the sharpness and the saturation difference (Δ
C *) and build-up property (L value) were measured, and the results are shown in Table 4.

[0057]

[Table 4]

From the evaluation results shown in Table 4, it can be seen that the ink-jet dyed carpet substrates of the present invention (Examples 9 and 10) have excellent sharpness and can obtain an ink-jet image with good chroma and build-up properties.

[0059]

The carpet base materials for ink jet dyeing of the present invention have good sharpness and build-up properties.
Clear images can be stained with good reproducibility. Therefore, by the dyeing method of the present invention, it is possible to obtain valuable printed products similar to high-grade printed products such as conventional roller printing and screen printing.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-311583 (JP, A) JP-A-5-148777 (JP, A) JP-A-5-179577 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) D06P 5/00 111 D06P 3/00

Claims (5)

(57) [Claims] Claims: 1. A water absorption capacity for pure water of 50 to 1,000.
A carpet base material for inkjet dyeing, wherein a water-insoluble water-absorbent resin of 0.1 ml / g is adhered to a carpet base material with a pile in an amount of 0.01 to 10% by weight. 2. The carpet base material for inkjet dyeing according to claim 1, wherein the carpet base material is a tufted carpet base material. 3. A carpet substrate, wherein a dispersion of a hydrophilic solvent of the water-insoluble water-absorbent resin or a mixed solvent of the hydrophilic solvent and water is treated by spraying, and the water-insoluble water-absorbent resin is adhered. Item 6. The carpet substrate for inkjet dyeing according to item 1 or 2. 4. A method of applying a water-insoluble water-absorbent resin to a piled carpet base material in an amount of 0.01 to 10% by weight, applying a dye ink by an ink jet method, and performing a heat fixing treatment. Inkjet dyeing method for carpet substrates. 5. The method according to claim 1, wherein the water-insoluble water-absorbent resin is dispersed in a hydrophilic solvent or a mixed solvent of water and a hydrophilic solvent, and the carpet base material is treated with a spray to adhere the water-insoluble water-absorbent resin. The inkjet dyeing method according to claim 4.