EP0605730B1 - Bedruckter stoff und verfahren zur herstellung - Google Patents

Bedruckter stoff und verfahren zur herstellung Download PDF

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Publication number
EP0605730B1
EP0605730B1 EP19930911977 EP93911977A EP0605730B1 EP 0605730 B1 EP0605730 B1 EP 0605730B1 EP 19930911977 EP19930911977 EP 19930911977 EP 93911977 A EP93911977 A EP 93911977A EP 0605730 B1 EP0605730 B1 EP 0605730B1
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Prior art keywords
cloth
water
dye
printed
dyes
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EP19930911977
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English (en)
French (fr)
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EP0605730A4 (de
EP0605730A1 (de
Inventor
Kazuo 939-37 Aza Narushima Oaza Zingo Kusaki
Toshikazu 245-48 Jyuri-Cho Fuse
Tohru 2-75 Nishi 5-Chome Morita
Toshihiko 21-15 Akashiadai 3-Chome Ishihara
Kazuyoshi 4-16 Koen-Cho Morimoto
Kazuo 1-39 Kanebo-Cho Iwata
Michiyo 249-5 Kiyotaki Nishimura
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Kanebo Ltd
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Kanebo Ltd
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Priority claimed from JP22075592A external-priority patent/JPH06145569A/ja
Priority claimed from JP4237795A external-priority patent/JP2607448B2/ja
Priority claimed from JP4293816A external-priority patent/JP2607450B2/ja
Application filed by Kanebo Ltd filed Critical Kanebo Ltd
Priority claimed from PCT/JP1993/000601 external-priority patent/WO1994002679A1/ja
Publication of EP0605730A1 publication Critical patent/EP0605730A1/de
Publication of EP0605730A4 publication Critical patent/EP0605730A4/de
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing

Definitions

  • the present invention relates to a printed cloth on which dyes are deposited in dots and a method for the preparation thereof.
  • Japanese Laid-Open Patent Publication No.6347 of 1986 describes that a fine pattern of deep color can be attained by performing dot dyeing so that a) the average of the major axis and the minor axis of the dot is 100 to 500 ⁇ m, b) the dot density is not higher than 16 dots/mm and c) the dots penetrate through the front surface to the back surface and part of the color points can be seen on the back surface of the cloth.
  • no deeper color can be attained than that attained by screen printing and not as a fine line as 0.3 mm or less can be attained as a printed pattern. It was also difficult to give an exact stripe pattern and a natural gradation pattern.
  • Japanese Patent Application No. 88 545 teaches a printing apparatus having an ink-jet recording head for the production of printed cloth.
  • EP-A-0 230 135 shows a multiple nozzle ink-jet dot printer for serial printing of symbols along a printing line on an information carrier, in accordance with a predetermined printing matrix, the head having a plurality of print elements, each provided with a nozzle for selectively projecting drops of ink on to the information carrier in print positions in accordance with the matrix.
  • JP-A-4-153380, JP-A-4-173178, JP-A-60-134085 and JP-A-63-72584 show methods for printing cloth via ink-jet printing.
  • the object of the present invention is to provide a printed cloth in which as a fine line as 0.3 mm or less, an exact stripe pattern, or a natural gradation pattern is clearly dyed in a deep color, which could not be attained by conventional methods.
  • the product of the present invention is one in which desired printed pattern is formed on a cloth by dyeing in dot a dye on it by a special ink jet process. It is characterized in claim 1.
  • the dyeing unit of the dot dyeing formed in as a very small line as 0.3 mm or less along the fiber to the longitudinal direction of the fiber with a thickness of the single fiber (about 0.01 to 0.1 mm). Therefore, each yarns constituting the cloth can be dyed in different colors as if they consist of different grandrelle yarns to obtain a product having fine lines, or an exact stripe pattern, which could not be accomplished up to now.
  • the printed pattern prepared by the present invention is basically formed by dot dyeing of very small line along the fiber as short as 0.3 mm or less to the longitudinal direction of the fiber with a thickness of the single fiber (about 0.01 to 0.1 mm).
  • a thickness of the single fiber about 0.01 to 0.1 mm.
  • present are the parts in which such fine linear dot dyeings are present each adjacent and a plural of the adjacent fibers are dyed to a same color and the part in which one dot dyeing is made over the adjacent fibers and each only half thicknesses of the adjacent fibers are dyed.
  • the product of the present invention can be prepared by a printing process according to ink jet methods as described in Japanese Patent Application No.278112 of 1990, No.298399 of 1990 and No.88545 of 1991. However, it is preferred to be formed by using dyes of the three primary colors or the three primary colors and a black color as the dyes. By using them, the present invention can express not less than 125 combined colors per unit pattern.
  • dyes including yellow, red (magenta) and blue (cyan) are used as the dyes of the three primary colors. It is preferred to use dyes (I to IV) having a perceived chromaticity index defined in CIE 1976 (L, a, b) space on the cloth of at least in the following range respectively as these dyes and the black dye.
  • These dyes may be used as a combination of at least two each colors.
  • the dyes of the following range can be also used in combination.
  • the color range which can be expressed by the three primary colors and the black color is within the range of the dotted line in Fig. 2A and a part of green, orange and violet can not be fully expressed in some cases. Therefore, in the case it is required to express these colors, it is preferred to use additionally at least one selected from orange (above VI), violet (above IX) and green (above X), particularly the dyes having the following a value and b value in addition to the dyes of the three primary colors and black color.
  • pretreat the cloth before dyed it is preferred to pretreat the cloth before dyed to prevent bleeding of the dye liquid.
  • a treatment is preferably made by calendering the cloth and/or by giving a water repellent finish to the cloth using a water repellent or a softening and water repellent to a water absorption of 5 to 240 seconds measured by JIS 1096A method or to a water repellency of 50 or lower measured by JIS L-1018.
  • the water repellents used include, for example, fluorine compounds, silicone compounds and zirconium compounds.
  • the softening and water repellents used include, for example, octadecylethyleneurea, zirconium acetate, polyolefine compounds, wax compounds and silicone compounds.
  • Fixing agents such as alkaline substances, e.g., sodium carbonate and sodium bicarbonate, and hydrotrope agents, e.g., urea, monomethylurea, dimethylurea, thiourea, monomethylthiourea, dimethylthiourea, formamide, dimethylformamide and dimehylacetamide may be also added to them.
  • Such a water repellent treatment may be carried out by using at least one selected from the above-mentioned water repellents and the softening and water repellents in combination with a sizing agent.
  • the sizing agents which can be used include, for example, water-soluble cellulose derivatives such as starch, soluble starch, water-soluble starch, water-soluble starch derivatives, carboxymethylcellulose, etherified carboxymethylcellulose, hydroxyethylcellulose and methylcellulose, gums such as sodium alginate, gum arabic, locust bean gum and guar gum, water-soluble proteins such as gelatin and glue, and water-soluble synthetic high polymers such as sodium polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyacrylamide, polyethyleneimine and quaternarized water-soluble cationic polymers.
  • the bleeding of the dye liquid can be more prevented by applying a breaking treatment in combination.
  • the water repellent and the softening and water repellent are applied to be adhered only on the outer surface of the cloth. In this case, it may be processed so that the water-absorbing agent is adhered on the back surface of the cloth where the water repellent and the softening and water repellent are not adhered.
  • the water-absorbing agent is not particularly restricted and, for example, a sizing agent and a water-absorbing silicone salt can be used.
  • a method for pretreating the cloth a method can be used in which a dye ink which can be adhered in dot during the printing is absorbed and maintained instantaneously on the surface of the cloth and a highly water-absorbent resin is adhered to prevent bleeding of the dye and color mixing.
  • the highly water-absorbent resins any of the commercially available highly water-absorbent resins can be used. It is preferred to use a graft-polymerized or partly crosslinked product of water-soluble polymers such as of starch type, protein type, cellulose type or synthetic polymer type which have an ability of maintaining 10 to 1000 times amount of water based on its weight.
  • the highly water-absorptive resin based on fibroin described in Japanese Patent Publication No. 57974 of 1983 can be used very effectively.
  • the highly water-absorptive resin can be used together with other treating agents and particularly it is preferred to be used together with a softening and water-repellent.
  • the dyes reactive dyes, acid dyes, direct dyes, dispersion dyes, cationic dyes and fluorescent dyes may be used in accordance with the type of the fiber of the cloth to be dyed. It is preferred that the dye liquid is prepared to have a surface tension of 0.030 to 0.065 N/m (30 to 65 dyne/cm) (particularly 0.040 to 0.050 N/m (40 to 50 dyne/cm)) and a viscosity of 4 mPas (4 cps) or less (particularly 1 to 2 mPas (1 to 2 cps)) at 25 °C.
  • the following dyes as the three primary color dyes and black dye as they give sure dye fastness after dyed.
  • the numbers show their CI numbers.
  • the dyes after removing inorganic salts, dispersing agents and solubilizers from them so that the dye liquid of very fine drops can be stably delivered in order to deposit the dye liquid on the cloth as a very small dots which can dye each single fibers in different colors.
  • a water-soluble dye in which the contents of sodium, potassium, phosphorus and copper are respectively controlled to be not higher than 0.01 % and the contents of the anionic surface active agent and the nonionic surface active agent are respectively controlled to be not higher than 0.015 %.
  • the contents of the mono- and divalent metal ions are controlled to be not higher than 10 ppm, it is preferred to use a water-soluble dye having a water solubility of not higher than 50 g/l at 20 °C.
  • the following dyes can be exemplified as such water-soluble dyes.
  • the numbers show their CI numbers.
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, thiodiethylene glycol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and polyethylene glycol dimethyl ether and urea as the dryness inhibitors in amounts of 100 to 300 g/l .
  • a reactive dye When a reactive dye is used, it is preferable to be used as an aqueous ink containing an alkyl ether derivative of a polyhydric alcohol prepared by etherifying the primary and secondary alcohol groups in the polyhydric alcohol.
  • a printing ink for ink jet consisting of 1 to 20 weight % of a reactive dye, 1 to 40 weight % of an alkyl ether derivative of a polyhydric alcohol mentioned above and 40 to 98 weight % of water.
  • Known hydrotrope agents and surface active agents may be added to the printing ink.
  • the orange, violet, green and navy blue dyes additively used together with the three primary color dyes include the followings.
  • the numbers show their CI numbers.
  • the printed cloth of the present invention is prepared by a procedure in which a cloth is pretreated as mentioned above and then a printing ink is sprayed on it to fix a desired printing pattern on it by an ink jet printing apparatus.
  • Such printing apparatus include, for example, an apparatus including an ink jet recording head as described in Japanese Patent Application No. 88545 of 1991.
  • a dye spraying apparatus which has nozzles of not less than 80 dots/cm (200 dpi), particularly not less than 120 dots/cm (300 dpi), for three primary colors, is controlled based on the image signal to print a desired image with the use of the three primary color dyes.
  • the ink jet methods include, for example, a bubble jet method in which a heating resistor element is buried in a nozzle and an ink is boiled by its heat and the ink is delivered by the pressure of the bubbles, a pulse jet method in which an electric, signal is applied on a piezoelectric element to deform it and the ink particles are blown by the excited volume change of the ink chamber, and an electric charge control method in which an ink is continuously pressure-sprayed from a nozzle vibrating by ultrasonic wave to particulate and the particles are controlled by the charge level and deviated by being passed through a definite electric field to be divided into recording particles and nonrecording particles.
  • a bubble jet method in which a heating resistor element is buried in a nozzle and an ink is boiled by its heat and the ink is delivered by the pressure of the bubbles
  • a pulse jet method in which an electric, signal is applied on a piezoelectric element to deform it and the ink particles are blown by the excited volume change
  • the dyeing is limited to 24 colors in the usual screen printing, unlimited colors can be easily realized in the present invention only by using the three primary colors or the three primary colors and black color or by adding a small number of dyes such as orange, violet, green and navy blue to them.
  • the dyeing can be carried out in dots for each single fiber unit of the yarn constituting the cloth.
  • the dot length is as fine as 0.3 mm or less to the longitudinal direction of the filament and therefore a product of highly natural appearance and deep color can be prepared as if it is prepared by using yarns made by twisting fibers dyed in band each other (that is grandrelle yarn) to express a fine printed pattern.
  • a deep color dyeing of high quality can be obtained.
  • a colored resist style product can be prepared by a procedure in which a dye ink containing a dye not decomposed by a reducing agent is applied on a cloth by ink jet method to form a printed pattern and then a reducing agent is applied on the printed pattern and the cloth is dyed with a reductively decolorizable dye.
  • a printed product of pepper-and-salt tone can be prepared by a procedure in which an original image of design is converted to a digital image data by an image input device and said image data is color separated by a color conversion device and then an ink jet device is controlled based on said separated image signals and random number signals to print the pattern on a cloth.
  • the preparation of an original picture can be made easily when a picture prepared by a procedure in which, when a pattern is drawn on the surface of a right-angled tetragon ABCD and the points internally dividing respectively a pair of the opposite sides AB and CD into a defined ratio m:n are defined to be E and F, said pattern is drawn so that it matches within an error of 0.3 mm or less on the segment BE and the segment DF or the segment AE and the segment CF, in both case that the segment BE and the segment DF are matched or that the segment AE and the segment CF are matched by rounding the tetragon into a cylinder so that the back surface of the tetragon ABCD comes inside is used as the original picture.
  • a repeated pattern of high degree of perfection suitable for digital processing by a computer can be obtained.
  • the cloths include woven fabrics, knitted fabrics and nonwoven fabrics.
  • the fibers constituting them may be natural fibers such as cotton, flax, wool and silk or synthetic fibers such as rayon, acetate, triacetate, Nylon, polyester and acrylic. They may be also their mixed fibers or union clothes.
  • the length of the fluff on the surface of the cloth is not more than 0.9 mm, the density of the fluff of 0.5 to 0.9 mm long is 15 fluffs/10 cm 2 or less and the density of the fluff of 0.5 mm long or shorter is 30 fluffs/10 cm 2 or less.
  • a treatment with a fluff binding agent an enzyme reduction treatment, double singeing treatment both on the raw cloth and on the scoured cloth, and shearing treatment after the preparations such as raw cloth singeing and scouring.
  • the fluff binding agents include, for example, water-soluble resins such as water-soluble polyester resin, polyvinyl alcohol, polyacrylic acid, casein, gelatin and thickner for printing, and emulsion resins such as hydrophilic polyester resin, vinyl compound polymers (polyvinyl acetate, polyvinyl acrylate resin and polyvinyl methyl resin).
  • water-soluble resins such as water-soluble polyester resin, polyvinyl alcohol, polyacrylic acid, casein, gelatin and thickner for printing
  • emulsion resins such as hydrophilic polyester resin, vinyl compound polymers (polyvinyl acetate, polyvinyl acrylate resin and polyvinyl methyl resin).
  • cellulose-decomposing enzymes such as cellulase and proteolytic enzymes such as protease can be used.
  • the singeing is carried out by a gas burner or by an electric heater.
  • the above-mentioned length of the fluff and the fluff density can be attained by a double singeing treatment both on the raw cloth and on the scoured cloth.
  • a shearing may be carried out in place of the second singeing.
  • Fig. 1 is an enlarged plan view showing the dyed condition in an example of a printed cloth according to the present invention.
  • Fig. 2 is a diagram showing an example of the color range which can be expressed according to the present invention.
  • the designation A shows the case of using three primary color dyes and black dye
  • the designation B shows a case of using orange, violet, green and navy blue dyes in addition to the three primary color dyes and black dye.
  • a cotton twill fabric in which each of warp and weft was #50 single yarn, a warp density was 52 warps/cm (130 warps/inch) and a weft density was 52 wefts/cm (130 wefts/inch), was singed, desized, scoured and bleached by usual methods.
  • the resultant cloth was padded by a treating solution consisting of the following composition and squeezed to a pick-up of 70 % and then dried at 100 °C for 2 minutes.
  • Yodosol PE-400 polyolefin resin manufactured by Kanebo N.S.C. Co.
  • the four color dye liquids as shown by the following 1 ⁇ to 4 ⁇ were fed in an ink jet printer of bubble jet type and three patterns of A to C were printed on the pretreated fabric to 16 dots/mm and then dried at 120 °C for 2 minutes.
  • the printed cloths were steamed at 108 °C for 20 minutes, washed and dried.
  • the desired printing pattern was clearly reproduced.
  • For the pattern A as a fine line as 0.3 mm was clearly dyed in different color each other.
  • the gradated pattern of B was clearly dyed in a more natural tone than general printing.
  • the stripe pattern of C was dyed by different colors clearly in lines.
  • the resultant cloth was treated in the same manner as in Example 1 to obtain a product having a clear printed pattern of deep colors in very natural appearance as in Example 1. It was also confirmed that the dyed condition on the fiber constituting the fabric was same as in the product of Example 1.
  • the resultant fabric was padded by an aqueous solution containing 0.3 part of a fluorine water repellent agent, Sumi Fluoil EM21 (manufactured by Sumitomo Kagaku Kogyo Co.) and 1 part of ammonium sulfate (pH controller) and then immediately squeezed by a mangle to a pick-up of 70 % and dried at 120 °C for 3 minutes.
  • a fluorine water repellent agent Sumi Fluoil EM21 (manufactured by Sumitomo Kagaku Kogyo Co.) and 1 part of ammonium sulfate (pH controller)
  • the above fabric was printed by an ink jet printer same as in Example 1 and dried at 120 °C for 2 minutes and then steamed by saturated steam at 102 °C for 30 minutes and washed.
  • Method A The same method as Method A was carried out except that the following four dyes were used in place of the six dyes used in Method A.
  • the printed pattern prepared by Method A could express a wide range of colors covering almost all range given by usual screen printing, while the printed pattern prepared by Method B was lower in concentration and narrower in the color range than those obtained by Method A.
  • the resultant cloth was padded by a treating solution consisting of the following composition and squeezed to a pick-up of 70 % and then dried at 120 °C for 2 minutes.
  • Duck Algin NSPH sodium alginate manufactured by Kibun Co.
  • Method A The same method as Method A was carried out except that the inks of Yellow 2, Red 2 and Blue 2 were not used but the four inks of Yellow 1, Red 1, Blue 1 and Black were used.
  • Method A The same method as Method A was carried out except that the inks of Yellow 1, Red 1 and Blue 1 were not used but the four inks of Yellow 2, Red 2, Blue 2 and Black were used.
  • a cotton plain fabric in which each of warp and weft was #50 single yarn, the warp density was 28.8 warps/cm (72 warps/inch) and the weft density was 28.8 wefts/cm (72 wefts/inch), was singed, desized, scoured, bleached and mercerized by usual methods.
  • the resultant cloth was padded by a treating solution consisting of the following composition and squeezed to a pick-up of 65 % and then dried at 120 °C for 2 minutes.
  • a resist paste of the following composition was printed only on the portion of the fabric where the prited pattern has been formed by using a screen printer and dried at 120 °C for 2 minutes.
  • Duck Algin NSPM medium viscosity sodium alginate manufactured by Kibun Co.
  • Resistol HWC resist for reactive dyes manufactured by Meisei Kagaku Kogyo Co.
  • a colored paste of the following composition was dyed on the fabric surface on which the resist paste was applied and dried at 120 °C for 2 minutes and then steamed by saturated steam at 102 °C 8 minutes, soaped and dried.
  • the pretreating agent, the dye ink, the resist paste and the colored paste used in Method A were stored at room temperature for two weeks and then the same fabric as in Method A was dyed and resisted in the same manner as in Method A.
  • a dye ink of the following composition was fed in a ink jet printer and the cloth dyed by the above liquid was printed by the dye ink in 8 dots/mm and dried at 120 °C for 2 minutes and then steamed by saturated steam at 102 °C for 8 minutes, soaped and dried.
  • CI Reactive Yellow 15 8 parts GCR-13 (resist for reactive dyes manufactured by Senka Co.) 8 parts Urea 5 parts Water 79 parts
  • the dye liquid and the dye ink used in Method C were stored at room temperature for two weeks and then the cloth was dyed and resisted in the same manner as in Method C.
  • the resultant cloth was padded by a treating solution (A) of the following composition containing a highly water-absorptive resin and squeezed to a pick-up of 80 % and then dried at 120 °C for 2 minutes.
  • Silk Polymer M (4 % aqueous solution of a highly water-absorptive resin, acrylic acid graft copolymer of silk fibroin, manufactured by Kanebo Co.) 4 parts Sodium carbonate ( fixing reactant ) 2 parts Water 94 parts
  • the printed fabric thus prepared was steamed by saturated steam at 105 °C for 10 minutes and washed.
  • Treating solution (B) was used in place of the treating solution (A).
  • Treating solution (B) Lite Gel A highly water-absorptive acrylic resin manufactured by Kyoeisha Yushi Kogyo Co., 40 % active
  • 10 parts Sodium carbonate (fixing reactant) 2 parts Water 88 parts
  • Method A The same method as in Method A was carried out except that no highly water-absorptive resin was added to the treating solution (A).
  • Method A The same method as in Method A was carried out except that 2 parts of Duck Algin NSPH (medium viscosity sodium alginate manufactured by Kibun Foods Co.) was used in place of the highly water-absorptive resin in the treating solution (A).
  • Duck Algin NSPH medium viscosity sodium alginate manufactured by Kibun Foods Co.
  • Method A The same method as in Method A was carried out except that 2 parts of Fine Gum HESK (modified carboxymethyl cellulose manufactured by Daiichi Kogyo Seiyaku Co.) was used in place of the highly water-absorptive resin in the treating solution (A).
  • Fine Gum HESK modified carboxymethyl cellulose manufactured by Daiichi Kogyo Seiyaku Co.
  • Methods A and B gave sharp pattern, high surface concentration of the dye, low penetration and low bleeding though printed three times to give printed cloths of very high quality.
  • the resultant cloth was padded by a treating solution of the following composition containing a highly water-absorptive resin and squeezed to a pick-up of 60 % and then dried at 120 °C for 2 minutes.
  • Sodium carbonate 2 parts Urea 5 parts Water 93 parts
  • the printed fabric thus prepared was steamed by saturated steam at 108 °C for 10 minutes, washed and dried.
  • the K/S values of the products prepare by Methods A to D were measured at the maximum absorption wave length of 520 nm by using a Macbeth spectrophotometer M-2020.
  • the periods required for the clogging of the nozzle when the fabric was ink jet printed by using the printing inks of Methods A to D were also measured. The results are shown in Table 4.
  • Methods A to D gave no nozzle clogging and showed good printing.
  • a printing ink containing an alkyl ether derivative of a polyhydric alcohol (Methods A to C) was used, the ink delivery was good to give a product of high dye fixation.
  • the resultant cloth was padded by a treating solution of the following composition and squeezed to a pick-up of 65 % and then one side of the cloth was dried by air flow at 120 °C for 3 minutes to migrate the treating solution to the dried surface.
  • Method A The same method as in Method A was carried out except that the pretreating solution was dried by a hot air flow at 120 °C for 2 minutes from the both sides of the plain woven fabric.
  • the following treating solution was padded to the resultant cloth and squeezed to a pick-up of 35 % and then dried by hot air flow at 120 °C for 3 minutes from one side of the woven fabric to migrate the treating solution to the dried surface side.
  • Disperse dye (CI Disperse Red 60) 5 parts Semol HT (dispersant manufactured by Nippon Senka Co.) 8 parts Ethylene glycol 5 parts Water 82 parts
  • Method C The same method as in Method C was carried out except that the pretreating solution was dried by hot air flow at 120 °C for 2 minutes from the both sides of the cloth.
  • Methods A and C in which a pretreating solution containing a water repellent was applied so that it was distributed only on the front surface side, gave very clear printed patterns of no bleeding and high penetration compared to Methods B and D in which the pretreating agent penetrated to the back surface side.
  • the following treating solution (1) was applied on one side of the resultant cloth by a knife overcoater and dried at 120 °C for 2 minutes and baked at 150 °C for 3 minutes. The amount of the water repellent adhered was 30 g/m 2 .
  • Treating solution (2) San Silicone-M (silicone water repellent manufactured by Sanyo Kasei Co., 30 % solid) 5 parts Duck Algin NSPM (medium viscosity sodium alginate manufactured by Kibun Co.) 2.5 parts Water 92.5 parts
  • ink consisting of the following compositions were respectively fed in an ink jet printer of pulse jet type and a continuous printing in 8 dots/mm was carried out on the cloth pretreated in two steps and then dried at 120 °C for 2 minutes and steamed by saturated steam at 102 °C for 10 minutes, washed and dried.
  • Ink (1) Reactive dye ( CI Reactive Blue 15 ) 10 parts Urea ( hydrotrope agent ) 5 parts Water 85 parts
  • Ink (2) Reactive dye ( CI Reactive Red 22 ) 10 parts Urea ( hydrotrope agent ) 5 parts Water 85 parts
  • Method A The same method as in Method A was carried out except that the treatment by the treating solution (1) [water repellent treating solution] was omitted.
  • Method A The same method as in Method A was carried out except that the pretreatment was carried out by one step method in which the treating solution (1) [water repellent treating solution] was padded on the cloth and then the cloth was squeezed to a pick-up of 65 % and dried at 120 °C for 2 minutes and baked at 150 °C for 3 minutes.
  • the treating solution (1) water repellent treating solution
  • Method A in which a water repellent was deposited only on the front surface of the cloth and a water absorber was deposited on the other portion showed no bleeding of the ink to give a printed cloth of sharp pattern, excellent color development and good quality.
  • the following treating solution was padded on the resultant cloth and squeezed to a pick-up of 65 % and dried at 120 °C for 2 minutes.
  • the woven fabric thus pretreated was broken by a Sanforizer (made by Sanforize Co.) at a speed of 20 m/min. and then an ink of the following composition was fed in an ink jet printer of pulse jet type and a continuous printing was carried out in 8 dots/mm on said woven fabric and the fabric was dried at 120 °C for 2 minutes and steamed by saturated steam at 102 °C for 8 minutes, washed and dried.
  • Reactive dye ( CI Reactive Blue 15 ) 10 parts
  • Method A The same method as in Method A was carried out except that a low temperature plasma treatment was carried out under an oxygen pressure of 66.5 Pa (0.5 Torr) at a plasma output of 2 kw for 20 minutes in place of breaking treatment by Sanforizing.
  • a plain 100 % cotton fabric in which each of warp and weft was #50 single yarn, the warp density was 54.4 warps/cm (136 warps/inch) and the weft density was 28.8 wefts/cm (72 wefts/inch), was singed, desized, scoured, bleached and mercerized by usual methods.
  • the following treating solution was padded on the resultant cloth and squeezed to a pick-up of 80 % and dried at 120 °C for 2 minutes.
  • Fine Gum HES (carboxymethyl cellulose manufactured by Daiichi Kogyo Seiyaku Co.) 0.5 parts FD Thickener 100 (water-soluble acrylic resin manufactured by Furukawa Kagaku Kogyo Co., 28 % solid) 3 parts Scotch Guard FC-214 (fluorinated water repellent manufactured by Sumitomo 3M Co., 15 % solid) 0.05 parts Sodium carbonate ( fixing reactant ) 3 parts Urea ( hydrotrope agent ) 5 parts Water 88.45 parts
  • Method A The same method as in Method A was carried out except that Viclon 90 (cationic softening agent manufactured by Ipposha Yushi Kogyo Co., 35 % solid) was used in place of Scotch Guard FC-214 in the pretreating agent.
  • Viclon 90 cationic softening agent manufactured by Ipposha Yushi Kogyo Co., 35 % solid
  • Methods A and B in which the cloth was pretreated with a treating solution containing carboxymethyl cellulose, a water-soluble acrylic resin (or a maleic acid resin) and a water repellent gave printed cloth of very high quality compared to other methods.
  • a plain 100 % cotton fabric in which each of warp and weft was #50 single yarn, the warp density was 54.4 warps/cm (136 warps/inch) and the weft density was 28.8 wefts/cm (72 wefts/inch), was singed, desized, scoured, bleached and mercerized by usual methods.
  • the following treating solution was padded on the resultant cloth and squeezed to a pick-up of 70 % and dried at 120 °C for 2 minutes.
  • TK Set 102 water-soluble polyester high molecular copolymer, fluff binder
  • Sodium bicarbonate dimethyl bicarbonate
  • Urea hydrootrope agent
  • Method A The same method as in Method A was carried out except that the pretreating solution in Method A was coated by a kiss roll applicator to 30 g/m 2 on wet basis and dried at 120 °C for 2 minutes.
  • Method B The same method as in Method B was carried out except that no fluff binder (TK Set 102) was added to the pretreating solution and the space between the cloth and the nozzle of the ink jet printer was made to be 1.5 mm.
  • TK Set 102 no fluff binder
  • the surface fluff was measured by the following method.
  • a cloth platform X consisting of a stainless steel sheet of 20 cm long, 20 cm wide and 10 mm thick having a projection of 10 mm long, 100 mm wide and 5 mm thick in the center of its surface and a weight sheet Y of 15 cm long, 15 cm wide and 5 mm thick having a hole of 11 mm long and 101 mm wide were prepared.
  • a test cloth was placed on said cloth platform X and the weight sheet Y was fit on it so that said hole got said projection to fix the test cloth on said projection.
  • a single laser beam irradiation apparatus was set at the position of the fluff length to be measured and the laser beam was irradiated on the fluffs and the beam was moved horizontally.
  • a plain 100 % silk woven fabric in which each of warp and weft was #50 single yarn, the warp density was 44 warps/cm (110 warps/inch) and the weft density was 30.4 wefts/cm (76 wefts/inch), was scoured and bleached by usual methods.
  • the following treating solution was padded on the resultant cloth and squeezed to a pick-up of 70 % and dried at 120 °C for 3 minutes.
  • Sumifluoil EM-21 manufactured by Sumitomo Kagaku Kogyo Co.
  • Ammonium sulfate 1 part Water 98.7 parts
  • An ink consisting of 30 parts of a dye solution purified as follows, 20 parts of diethylene glycol and 50 parts of water was fed in an ink jet printer of pulse jet type and a continuous printing in 8 dots/mm was carried out on the cloth thus pretreated and the cloth was dried at 120 °C for 2 minutes and steamed by saturated steam at 102°C for 10 minutes, washed and dried.
  • the above-mentioned dye solution was prepared by purifying an acid dye (CI Acid Red 289) in two steps as follows.
  • ES771 (amine exchanging group type phenolic resin manufactured by Sumitomo Kagaku Kogyo Co.) was washed with water and converted to -OH type with sodium hydroxide and further washed with water. 450 g of the resultant adsorbing resin was added to a 15 % aqueous solution of said dye and the mixture was stood for 8 hours and then filtered to remove the resin and dried to purify the dye. The purification was repeated 5 times to decrease the contents of the anionic and nonionic surface active agents respectively to 0.015 % or lower on dye powder basis.
  • a 15 % aqueous solution of the dye purified above was prepared and the dye was further purified by using an RO Minitester (made by Teijin Engineering Co., membrane: B-21 type, M.W.:1000). The purification was repeated 5 times to decrease the contents of calcium, potassium, phosphorus and copper respectively to 0.01 % or lower on dye powder basis.
  • the dye was purified by only the method (1) of removing the surface active agents.
  • the dye contained 4.0 % sodium, 0.02 % calcium, 0.02 % potassium, 0.2 % phosphorus and 0.2 % copper.
  • the dye was purified by only the method (2) of removing sodium and others.
  • the dye contained 0.03 % of the anionic surface active agent and 0.03 % of the nonionic surface active agent.
  • Method A using the dye purified in two steps of (1) and (2) gave small nondelivery number of ink and the product was excellent in jet stability to prepare a printed product of high quality.
  • dot dyeing units are formed in very small line along the fiber to a thickness of monofilament (ca. 0.01 to 0.1 mm) and to a longitudinal length of 0.3 mm or shorter. Therefore, a printed cloth of very natural appearance in which the yarns constituting the cloth are dyed in different colors as if each of them consists of different grandrelle yarn. As fine a line as 0.3 mm which could not obtained up to now can be dyed clearly in different colors and a product of exact stripe pattern or having gradation pattern of complex combination of a variety of colors can be prepared surely.
  • the dye does not penetrate to the back surface of the cloth and deposits on the front surface of the cloth clearly and thus a deep dyeing can be achieved.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Claims (21)

  1. Ein bedruckter Stoff, wobei ein Farbstoff in Punkten auf dem Stoff abgeschieden wird, so daß ein erwünschtes Druckmuster gebildet wird, dadurch gekennzeichnet, daß die Punktabscheidung in einer Länge von 0,05 bis 0,3 mm in Längsrichtung jeder aus Fasern gebildeten Garne des Stoffs gebildet wird, so daß die Garne in Jaspé-Form gefärbt werden und der Farbstoff eindeutig auf der Stoffobeifläche abgeschieden wird, ohne auf die Rückseite des Stoffes durchzudringen.
  2. Ein bedruckter Stoff gemäß Anspruch 1, wobei das Druckmuster durch Verwendung von Farbstoffen aus den drei Grundfarben oder den drei Grundfarben und Schwarzfarbe gebildet wird.
  3. Ein bedruckter Stoff gemäß Anspruch 2, wobei die Farbstoffe I, II und III, die einen wahrgenommenen Farbindex (a) und (b), der im Farbbereich [CIE 1976 (L,a,b)-Farbraum] definiert ist, auf dem Stoff innerhalb des folgenden Bereichs besitzen, als die Farbstoffe der drei Grundfarben verwendet werden und Farbstoff IV als der schwarze Farbstoff verwendet wird. I Gelb (a) -20∼0 (b) 50∼90 II Rot (a) 50∼70 (b) 0∼20 III Blau (a) -50∼-10 (b) -50∼-20 IV Schwarz (a) -6∼6 (b) -6∼6
  4. Ein bedruckter Stoff gemäß Anspruch 3, wobei wenigstens ein Farbstoff, ausgewählt aus den Farbstoffen V bis XI mit einem wahrgenommenen Farbindex (a) und (b) innerhalb des folgenden Bereichs, zusätzlich zu den oben genannten Farbstoffen I bis IV verwendet wird. V Gelb (a) 0∼20 (b) 50∼90 VI Gelb (a) 20∼70 (b) 40∼90 VII Rot (a) 50∼70 (b) -20∼0 VIII Blau (a)-10~20 (b)-50~20 IX Violett (a) 20~70 (b) -50~-20 X Grün (a) -70~-20 (b) 50~90 XI Marineblau : (a) -10~10 (b) -20~5
  5. Ein bedruckter Stoff gemäß Anspruch 1, wobei so feine Linien wie 0,3 mm oder weniger dick in verschiedenen Farben durch die oben genannte Abscheidung in Punkten als Färbung auf dem Stoff aufgetragen werden.
  6. Ein bedruckter Stoff gemäß Anspruch 1, wobei der Stoff durch Verwendung eines wasserabweisenden Mittels oder eines weichmachenden wasserabweisenden Mittels wasserabweisend gemacht wird und die Wasserabsorption 5 bis 240 Sekunden gemäß JIS 1096A beträgt oder das Wasserabweisungsvermögen 50 oder weniger gemäß JIS L1018 beträgt.
  7. Ein bedruckter Stoff gemäß Anspruch 1, wobei der Stoff durch Verwendung wenigstens eines Mittels, ausgewählt aus der Gruppe, bestehend aus wasserabweisenden Mitteln und weichmachenden wasserabweisenden Mitteln sowie einem Schlichtemittel, bearbeitet wird.
  8. Ein bedruckter Stoff gemäß Anspruch 7, wobei wenigstens ein Mittel, ausgewählt aus der Gruppe, bestehend aus wasserabweisenden Mitteln und weichmachenden wasserabweisenden Mitteln sowie einem Schlichtemittel, nur auf der Vorderseite des Stoffs abgeschieden wird.
  9. Ein bedruckter Stoff gemäß Anspruch 7, wobei wenigstens ein Mittel, ausgewählt aus der Gruppe, bestehend aus wasserabweisenden Mitteln und weichmachenden wasserabweisenden Mitteln sowie einem Schlichtemittel, nur auf der Vorderseite des Stoffs abgeschieden wird und ein wasserabsorbierendes Mittel auf der Rückseite des Stoffs abgeschieden wird.
  10. Ein bedruckter Stoff gemäß Anspruch 1, wobei der Stoff behandelt wird, indem (1) wenigstens ein Element, ausgewählt aus der Gruppe, bestehend aus Carboxymethylcellulose, einer veretherten Carboxymethylcellulose und Natriumalginat, (2) wenigstens ein Element, ausgewählt aus der Gruppe, bestehend aus einem wasserlöslichen Acrylharz und einem Maleinsäureharz, und (3) wenigstens ein Element, ausgewählt aus der Gruppe, bestehend aus einem wasserabweisenden Mittel und einem weichmachenden wasserabweisenden Mittel, verwendet werden.
  11. Ein bedruckter Stoff gemäß Anspruch 1, wobei der Stoff durch Verwendung eines stark wasserabsorbierenden Harzes bearbeitet wird.
  12. Ein Verfahren zur Herstellung eines bedruckten Stoffs, bei dem eine farbstoffhaltige Drucktinte in Punkten auf der Oberfläche eines Stoffs abgeschieden wird, dadurch gekennzeichnet, daß ein Stoff mit wenigstens einem wasserabweisenden Mittel behandelt wird und die Drucktinte dann mit einem Tintenstrahldrucker, der eine Düse mit 80 Punkten/cm oder mehr besitzt und anhand des Bildsignals gesteuert wird, auf den Stoff gedruckt wird, wobei der Farbstoff in einer Länge von 0,05 bis 0,3 mm in Längsrichtung jeder aus Fasern gebildeten Garne des Stoffs abgeschieden, so daß die Garne in Jaspé-Form gefärbt werden, und eindeutig auf der Stoffoberfläche abgeschieden wird, ohne auf die Rückseite des Stoffes durchzudringen.
  13. Ein Verfahren gemäß Anspruch 12, bei dem der Stoff mit wenigstens einem wasserabweisenden Mittel und wenigstens einem Schlichtemittel behandelt wird und die Drucktinte dann mit dem Tintenstrahldrucker auf den Stoff gedruckt wird.
  14. Ein Verfahren gemäß Anspruch 13, bei dem der mit dem wasserabweisenden Mittel und dem Schlichtemittel behandelte Stoff einer Bruchbehandlung unterworfen wird und die Drucktinte dann mit dem Tintenstrahldrucker auf den Stoff gedruckt wird.
  15. Ein Verfahren gemäß Anspruch 13, bei dem das wasserabweisende Mittel auf der Vorderseite des Stoffs abgeschieden wird und das Schlichtemittel auf der Rückseite des Stoffs abgeschieden wird.
  16. Ein Verfahren gemäß Anspruch 13, bei dem der Stoff durch Verwendung eines wasserabweisenden Mittels zusammen mit (1) wenigstens einer Verbindung, ausgewählt aus der Gruppe, bestehend aus Carboxymethylcellulose, veretherter Carboxymethylcellulose und Natriumalginat, und (2) wenigstens einem Harz, ausgewählt aus der Gruppe, bestehend aus wasserlöslichen Acrylharzen und Maleinsäureharzen, behandelt wird und die Drucktinte dann auf den behandelten Stoff gedruckt wird.
  17. Ein Verfahren gemäß Anspruch 12, bei dem die Drucktinte einen wasserlöslichen Farbstoff enthält und die Gehalte an Natrium, Calcium, Phosphor und Kupfer jeweils auf 0,01 % oder weniger eingestellt werden und die Gehalte an anionischen und nichtionischen oberflächenaktiven Mitteln jeweils auf 0,015% oder weniger eingestellt werden.
  18. Ein Verfahren gemäß Anspruch 12, bei dem der Farbstoff ein wasserlöslicher Farbstoff ist, der eine Wasserlöslichkeit (bei 20°C) von 50 g/l oder höher besitzt, wenn die Gehalte an monovalenten und bivalenten Metallen auf 10 ppm oder weniger eingestellt werden.
  19. Ein Verfahren gemäß Anspruch 12, bei dem die Drucktinte 1 bis 20 Gew.-% eines Reaktionsfarbstoffs, 1 bis 40 Gew.-% eines Alkylethers eines mehrwertigen Alkohols, hergestellt durch Verethern der primären und sekundären Alkoholgruppen eines mehrwertigen Alkohols, und 40 bis 98 Gew.-% Wasser enthält.
  20. Ein Verfahren gemäß Anspruch 12, bei dem die Oberfläche des Stoffs mit einem wasserabweisenden Mittel oder einem weichmachenden wasserabweisenden Mittel behandelt wird, um die Wasserabsorption auf 5 bis 240 Sekunden gemäß JIS 1096A oder das Wasserabweisungsvermögen auf 50 oder weniger gemäß JIS L1018 einzustellen, und anschließend die Drucktinte aufgetragen wird.
  21. Ein Verfahren zur Herstellung eines bedruckten Stoffs, bei dem eine farbstoffhaltige Drucktinte in Punkten auf der Oberfläche eines Stoffs abgeschieden wird, dadurch gekennzeichnet, daß ein Stoff mit einem stark wasserabsorbierenden Harz behandelt wird, das in der Lage ist, die 10- bis 1000fache Menge an Wasser, bezogen auf sein Gewicht, aufzunehmen, und anschließend die Drucktinte mit einem Tintenstrahldrucker, der eine Düse mit 80 Punkten/cm oder mehr besitzt und anhand des Bildsignals gesteuert wird, auf den Stoff gedruckt wird, wobei der Farbstoff in einer Länge von 0,05 bis 0,3 mm in Längsrichtung jeder aus Fasern gebildeten Garne des Stoffs auf dem Stoff abgeschieden, so daß die Garne in Jaspé-Form gefärbt werden, und eindeutig auf der Stoffoberfläche abgeschieden wird, ohne auf die Rückseite des Stoffes durchzudringen.
EP19930911977 1992-07-27 1993-04-30 Bedruckter stoff und verfahren zur herstellung Expired - Lifetime EP0605730B1 (de)

Applications Claiming Priority (13)

Application Number Priority Date Filing Date Title
JP22075592A JPH06145569A (ja) 1992-07-27 1992-07-27 インクジェット捺染用インク
JP22075592 1992-07-27
JP220755/92 1992-07-27
JP23648992 1992-08-11
JP236489/92 1992-08-11
JP23648992 1992-08-11
JP23779592 1992-08-12
JP4237795A JP2607448B2 (ja) 1992-08-12 1992-08-12 インクジェット捺染方法
JP237795/92 1992-08-12
JP4293816A JP2607450B2 (ja) 1992-10-06 1992-10-06 インクジェット捺染用布帛およびその捺染法
JP29381692 1992-10-06
JP293816/92 1992-10-06
PCT/JP1993/000601 WO1994002679A1 (en) 1992-07-27 1993-04-30 Printed cloth and method of manufacturing the same

Publications (3)

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EP0605730A1 EP0605730A1 (de) 1994-07-13
EP0605730A4 EP0605730A4 (de) 1998-05-13
EP0605730B1 true EP0605730B1 (de) 2005-11-30

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DE69432675T2 (de) * 1993-07-09 2004-04-15 Canon K.K. Druckverfahren, Druck und durch diesem hergestellte Artikel
JP3021240B2 (ja) * 1993-07-09 2000-03-15 キヤノン株式会社 インクジェットプリント方法、及び、プリント物
US5867197A (en) * 1994-07-21 1999-02-02 Canon Kabushiki Kaisha Ink-jet printing cloth, ink-jet printing process and production process of print
JPH08176973A (ja) * 1994-10-25 1996-07-09 Canon Inc インクジェット捺染方法および捺染物
AU1550597A (en) * 1996-01-23 1997-08-20 A W Hainsworth & Sons Limited Improvements in and relating to cloth
JPH09279489A (ja) * 1996-02-15 1997-10-28 Canon Inc インクジェット捺染用布帛、インクジェット捺染方法および捺染物
US6200667B1 (en) * 1997-03-24 2001-03-13 Canon Kabushiki Kaisha Cloth for textile printing, and textile printing process using the cloth and print obtained thereby
US6511535B1 (en) 1998-07-08 2003-01-28 Ciba Specialty Chemicals Corporation Method for printing fibrous textile materials using the ink jet technique
JP3582434B2 (ja) 1998-12-17 2004-10-27 セイコーエプソン株式会社 インクジェット捺染用インク組成物
US6838498B1 (en) * 1999-11-04 2005-01-04 Kimberly-Clark Worldwide, Inc. Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention
EP1914343B1 (de) 1999-11-04 2012-09-12 Kimberly-Clark Worldwide, Inc. Beschichtung zur Behandlung von Substraten für Tintenstrahldruck , Verfahren zur Behandlung dieser Substrate und daraus hergestellte Artikel
CA2390040C (en) 2000-01-19 2010-12-21 Kimberly-Clark Worldwide, Inc. Waterfast ink receptive coatings for ink jet printing materials and coating methods therewith
US6936648B2 (en) 2000-10-30 2005-08-30 Kimberly-Clark Worldwide, Inc Coating for treating substrates for ink jet printing including imbibing solution for enhanced image visualization and retention, method for treating said substrates, and articles produced therefrom
US7270651B2 (en) 2001-12-19 2007-09-18 The Procter & Gamble Company Absorbent article
US7402157B2 (en) 2001-12-19 2008-07-22 The Procter & Gamble Company Absorbent article having perception of depth
US7306582B2 (en) 2001-12-19 2007-12-11 The Procter & Gamble Company Absorbent article
US8716548B2 (en) 2002-02-20 2014-05-06 The Procter & Gamble Company Disposable absorbent article designed to facilitate an easy change
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WO2005033211A1 (ja) 2003-10-01 2005-04-14 Nippon Kayaku Kabushiki Kaisha アゾ化合物、それを用いた染料水溶液、インク及びその用途
US20150057632A1 (en) 2013-08-23 2015-02-26 The Procter & Gamble Company Absorbent Article
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