EP1995374A2 - Mittels kationischer Farbstoffe gefärbte Textilprodukte und Verfahren zu ihrer Herstellung - Google Patents
Mittels kationischer Farbstoffe gefärbte Textilprodukte und Verfahren zu ihrer Herstellung Download PDFInfo
- Publication number
- EP1995374A2 EP1995374A2 EP20080380142 EP08380142A EP1995374A2 EP 1995374 A2 EP1995374 A2 EP 1995374A2 EP 20080380142 EP20080380142 EP 20080380142 EP 08380142 A EP08380142 A EP 08380142A EP 1995374 A2 EP1995374 A2 EP 1995374A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- cotton
- dyeing
- fabric
- bath
- direct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000000975 dye Substances 0.000 title claims description 69
- 239000004753 textile Substances 0.000 title description 4
- 239000004744 fabric Substances 0.000 claims abstract description 59
- 238000004043 dyeing Methods 0.000 claims abstract description 57
- 229920000742 Cotton Polymers 0.000 claims abstract description 38
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 16
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 2
- 238000010014 continuous dyeing Methods 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims 4
- 239000004909 Moisturizer Substances 0.000 claims 1
- 230000001333 moisturizer Effects 0.000 claims 1
- 239000003086 colorant Substances 0.000 abstract description 10
- 241001062009 Indigofera Species 0.000 description 11
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 11
- 229940097275 indigo Drugs 0.000 description 9
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/62—Natural or regenerated cellulose using direct dyes
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/0004—General aspects of dyeing
- D06P1/002—Processing by repeated dyeing, e.g. in different baths
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
Definitions
- Dyes are colored organic substances which are used to dye other objects, are soluble in acid, neutral or basic media, and possess an unsaturated molecular structure; that is, they are electronically unstable so they react with the material to be dyed, becoming fixed in the latter.
- the endurance or strength of a dye can vary when it is applied to different fibers. Even though the use of a given dye is properly determined, the strength thereof varies, depending on the dyeing process used. Thus, depending on the fiber to be dyed and the final use of the fabric or knitting, the suitable type of dye and the suitable dyeing process should be chosen in order to obtain the desired results.
- the present invention relates specifically to the dyeing of cotton and blends thereof (polyester, acrylics, Tencel® (a cellulose fabric that is obtained by an organic solvent spinning process)) in colors which are different from indigo, by means of a direct, cationic dye commonly used for paper dyeing, such that bright and clean dyes are obtained with a proper behavior to wash down, achieving the desired worn-out in fabrics used for the manufacture of socalled "jeans".
- a direct, cationic dye commonly used for paper dyeing such that bright and clean dyes are obtained with a proper behavior to wash down, achieving the desired worn-out in fabrics used for the manufacture of socalled “jeans”.
- a process suitable for achieving this type of dyeing is also disclosed.
- a dye known as indigo is generally used for the dyeing of the fiber or yarn used in the manufacture of fabrics for making jeans, or for the dyeing of a knitted fabric, thus obtaining satisfactory results both for the dyed fabric as well as a washed down fabric.
- the use of indigo is limited to blue jeans. Up to this date, and even though the existing demand so requires, it has not been possible to obtain a fabric suitable for the manufacture of colored jeans, which exhibits brightness and the proper color both before and after wash down. In the manufacture of jeans and denim garments, it is common to combine in the same garment both a washed down fabric and a non washed down fabric, thus making apparent the importance of the characteristics of the fabric both before and after the wash down.
- EP 0 343 925 in the name of Mitsui Toatsu Chemicals, relates to obtaining a colored denim fabric by means of a dyeing bath containing a dye or a dye blend with an indigo, so to obtain in the final product a behavior similar to that of indigos, also exhibiting the discoloring effect similar to when indigo is bleached with a chlorine solution.
- EP 0 342 925 it is not possible to obtain the full range of desired colors, since the dye is blended with indigo, in addition to the fact that the obtained colors are not entirely clean nor have the brightness achieved with the dyes and the process of the present invention.
- Cationic dyes are organic compounds which can be positively charged (cations) or negatively charged (anions).
- Cationic dyes are joined to the fibers by means of forming salt bonds with the anionic groups or the acid groups of the fibers and posses a very high dyeing power. Generally, they are used to dye paper, synthetic fibers and even human hair, since a bright coloring and a deep dyeing are achieved.
- Direct, cationic dyes had never before been used to dye fabric, fibers or yarn for the manufacture of fabric, for the manufacture of colored jeans, since as a result of obtaining so deep colors, the fabric does not react properly to wash down.
- cationic dyes have been traditionally considered in industry as unsuitable for cotton fibers, yarn or fabrics, including those cases where cotton is blended with other fibers, particularly synthetic fibers.
- the present invention relates to the use of direct, cationic dyes to dye fabrics, fibers or yarn made of cotton or cotton blends with synthetic fibers, for the manufacture of fabric, by means of any known dyeing process, using a direct, cationic dye, so that, controlling process variables such as temperatures, pH, concentration and exposure time, fabric with clean colors and the desired brightness is achieved, which suitably reacts to wash down.
- a fabric of these characteristics has not been nor is currently available in the market.
- JP 09316785 in the name of Sumitomo Chemical Co., relates to a method of dyeing cellulose fiber by means of a cationic dye, to achieve a sufficiently deep and clear color; in order to achieve this purpose, cellulose is pre-treated with a sulphur containing compound.
- Patent 5,766,269 assigned to Clariant, discloses a type of cationic dye obtained by means of cationization of a sulphur dye with a compound comprising at least an amino group of a basic nature; the dyes thus obtained are used to dye acrylic fibers, cellulosic fibers, wool, silk and, mainly, leather. None of the above-mentioned patents even contemplates the behavior of the fabric to wash down nor the suitable dyeing process to achieve a fabric having the suitable brightness, the clean nature and the behavior to wash down for the manufacture of colored jeans.
- the present invention also relates to a method for dyeing fibers, yarn or fabrics made of cotton or cotton blends with synthetic fibers, by means of a direct, cationic dye which does not derive from nor contains sulphur, so to obtain a final product with a bright and clean dyeing and which can be washed down in processes or process steps after the dyeing in order to achieve the worn-out effect sought for fabrics used in the manufacture of jeans. Also described is the product obtained by means of this method.
- An object of the present invention is obtaining a suitable fabric for the manufacture of colored jeans with an unsurpassable brightness and a suitable behavior to wash down.
- Another object of the present invention is obtaining the range of colors not previously obtained with the described characteristics of brightness and behavior to wash down.
- a further object of the present invention is the use of direct, cationic dyes for obtaining a fabric with the described brightness, color and behavior to wash down.
- An additional object of the present invention is to provide a suitable method for obtaining the described fabric.
- Dyes can be classified in several manners, according to their application, according to their chemical nature, etc.
- direct dyes can be found, which, as their name indicates, can be directly applied to the material to be dyed without the need of any adjuvant agent, as well as indirect dyes, which require the aid of compounds called mordants in order to be fixed to the material to be dyed.
- indirect dyes which require the aid of compounds called mordants in order to be fixed to the material to be dyed.
- anionic dyes and cationic dyes depending on the ionic character of its reactive group or groups.
- a direct cationic dye is one the reactive groups of which are positively charged ions and which is used directly in the dyeing bath without the need of any type or vehicle or pre-treatment for the fiber for the dye to be fixed to the fiber.
- a direct, cationic dye is attached to the fibers by means of forming salt bonds with the anionic or acid groups of the fibers and has a very high dyeing power.
- the present invention describes the dyeing of fibers, yarn or fabrics made of cotton or blends of cotton with synthetic fibers, using a direct, cationic dye.
- the material to be dyed that is fiber, yarn or fabric, is passed through a bath to remove natural impurities attached to the fibers, consisting of a water solution containing a cationic moisturizing agent in a concentration of about 2-10 g/l, the temperature of the bath varying between about 40 and 90°C, and the immersion time between about 10 and 30 seconds; the material is squeezed so that it has an absorption capacity after being squeezed, or "pick up", of between about 60 and 80% of its own weight.
- a bath to remove natural impurities attached to the fibers consisting of a water solution containing a cationic moisturizing agent in a concentration of about 2-10 g/l, the temperature of the bath varying between about 40 and 90°C, and the immersion time between about 10 and 30 seconds; the material is squeezed so that it has an absorption capacity after being squeezed, or "pick up", of between about 60 and 80% of its own weight.
- the material is rinsed with water at a temperature of between about 40 and 80°C, passed to second rinsing step at room temperature; once it is rinsed, the material is squeezed until it achieves an absorption capacity (pick up) of about 150 to 300% of its own weight.
- the dyeing bath is prepared mixing the direct, cationic dye with water at a temperature of between about 60 and about 95°C; the pH of the bath should be kept between about 4 and 9; in order to keep the pH within the indicated range, it is possible to use a buffer solution.
- the concentration of the dye varies between about 0.05 and 500 g/l, depending on the intensity of the color hue desired in the final product.
- This dyeing bath can be used in any known dyeing process, such as dyeing by depletion the yarn, fiber, fabric or garment, continuous dyeing of the fabric, dyeing the yarn in width and in cord, or any type of dyeing process by immersion.
- the material to be dyed can be passed through more than a single immersion tank, depending on the desired fixation and color.
- the immersion time varies between about 10 and 30 seconds.
- the dyed material is rinsed with water at room temperature in order to remove the dye not fixed to the fiber and then passed to a fixation bath containing an anionic fixation agent, such as an arylsulfonate, in a concentration of about 80 to 120 g/l, with a residence time of about 30 to 60 seconds. Finally, the material is rinsed again with water at room temperature, obtaining the material -either fiber, yarn or fabric- dyed with the desired color and brightness and ready for subsequent processing.
- an anionic fixation agent such as an arylsulfonate
- the dyeing in the case of fibers, they are used to manufacture yarn and subsequently fabric; in the case of yarn, fabric is made therewith, so that the final product is a fabric with the desired color and brightness and which, in addition, can be washed down.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| MXPA07005607 | 2007-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1995374A2 true EP1995374A2 (de) | 2008-11-26 |
Family
ID=39827146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20080380142 Withdrawn EP1995374A2 (de) | 2007-05-09 | 2008-05-08 | Mittels kationischer Farbstoffe gefärbte Textilprodukte und Verfahren zu ihrer Herstellung |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP1995374A2 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113550047A (zh) * | 2021-08-18 | 2021-10-26 | 浙江美欣达纺织印染科技有限公司 | 仿靛蓝牛仔面料及生产方法 |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457002A (en) | 1965-12-27 | 1969-07-22 | Baird Atomic Inc | Variable monochromator with cylindrical interference wedge |
| US4131423A (en) | 1976-12-02 | 1978-12-26 | Ise Kagaku Kogyo Kabushiki Kaisha | Process for dyeing cellulose fibers with vat or sulfur dyes and oxyhalogen acid |
| US4166715A (en) | 1978-03-13 | 1979-09-04 | Huckaby Leonard L | Oil well pumping tube drain device |
| US4288589A (en) | 1978-06-30 | 1981-09-08 | Ciba-Geigy Corporation | Cationic dyes |
| US4322214A (en) | 1979-04-18 | 1982-03-30 | Asahi Chemical Company Limited | Dyeing method |
| US4536907A (en) | 1982-11-29 | 1985-08-27 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for effecting an accelerated neutralization of cellulose textile substrates impregnated with alkaline hydroxide |
| EP0342925A2 (de) | 1988-05-17 | 1989-11-23 | Seiko Epson Corporation | Anzeigetafel mit aktiver Matrix |
| EP0343925A2 (de) | 1988-05-25 | 1989-11-29 | MITSUI TOATSU CHEMICALS, Inc. | Farbstoffzusammenstellungen für das Färben von Denim-Baumwollegarnen |
| JPH02170861A (ja) | 1988-12-23 | 1990-07-02 | Mitsui Toatsu Chem Inc | ロープ染色用染料、これを用いる染色法、ならびに染色物 |
| EP0408269A2 (de) | 1989-07-10 | 1991-01-16 | MITSUI TOATSU CHEMICALS, Inc. | Strangfärbeverfahren mit Indigoderivat und hergestellter gefärbter Artikel |
| WO1993007221A1 (en) | 1991-10-11 | 1993-04-15 | Sandoz Ltd. | Sulphur dye compositions and their production |
| US5295998A (en) | 1993-02-02 | 1994-03-22 | Liquid Carbonic Industries Corporation | Adjusting pH in dyeing processes using CO2 |
| EP0741168A1 (de) | 1995-05-03 | 1996-11-06 | Clariant Finance (BVI) Limited | Schwefelfarbstoffe |
| JPH09316785A (ja) | 1996-05-29 | 1997-12-09 | Sumitomo Chem Co Ltd | カチオン染料によるセルロース系繊維の染色又は捺染方法 |
| US5766269A (en) | 1995-03-10 | 1998-06-16 | Clariant Finance (Bvi) Limited | Cationic dyes, their production and use |
| WO2000036211A1 (en) | 1998-12-17 | 2000-06-22 | Clariant Finance (Bvi) Limited | Dyeing process and dye composition |
| WO2004012406A1 (en) | 2002-07-29 | 2004-02-05 | Research In Motion Limited | System and method of mimetic messaging settings selection |
| WO2005012437A1 (en) | 2003-07-24 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | Cationic direct dyes |
| US20060059635A1 (en) | 2004-02-18 | 2006-03-23 | Melvin Alpert | Method for dyeing fabric materials with indigo, other vat dyes, and sulfur dyes |
-
2008
- 2008-05-08 EP EP20080380142 patent/EP1995374A2/de not_active Withdrawn
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457002A (en) | 1965-12-27 | 1969-07-22 | Baird Atomic Inc | Variable monochromator with cylindrical interference wedge |
| US4131423A (en) | 1976-12-02 | 1978-12-26 | Ise Kagaku Kogyo Kabushiki Kaisha | Process for dyeing cellulose fibers with vat or sulfur dyes and oxyhalogen acid |
| US4166715A (en) | 1978-03-13 | 1979-09-04 | Huckaby Leonard L | Oil well pumping tube drain device |
| US4288589A (en) | 1978-06-30 | 1981-09-08 | Ciba-Geigy Corporation | Cationic dyes |
| US4322214A (en) | 1979-04-18 | 1982-03-30 | Asahi Chemical Company Limited | Dyeing method |
| US4536907A (en) | 1982-11-29 | 1985-08-27 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process for effecting an accelerated neutralization of cellulose textile substrates impregnated with alkaline hydroxide |
| EP0342925A2 (de) | 1988-05-17 | 1989-11-23 | Seiko Epson Corporation | Anzeigetafel mit aktiver Matrix |
| EP0343925A2 (de) | 1988-05-25 | 1989-11-29 | MITSUI TOATSU CHEMICALS, Inc. | Farbstoffzusammenstellungen für das Färben von Denim-Baumwollegarnen |
| JPH02170861A (ja) | 1988-12-23 | 1990-07-02 | Mitsui Toatsu Chem Inc | ロープ染色用染料、これを用いる染色法、ならびに染色物 |
| EP0408269A2 (de) | 1989-07-10 | 1991-01-16 | MITSUI TOATSU CHEMICALS, Inc. | Strangfärbeverfahren mit Indigoderivat und hergestellter gefärbter Artikel |
| WO1993007221A1 (en) | 1991-10-11 | 1993-04-15 | Sandoz Ltd. | Sulphur dye compositions and their production |
| US5295998A (en) | 1993-02-02 | 1994-03-22 | Liquid Carbonic Industries Corporation | Adjusting pH in dyeing processes using CO2 |
| US5766269A (en) | 1995-03-10 | 1998-06-16 | Clariant Finance (Bvi) Limited | Cationic dyes, their production and use |
| EP0741168A1 (de) | 1995-05-03 | 1996-11-06 | Clariant Finance (BVI) Limited | Schwefelfarbstoffe |
| JPH09316785A (ja) | 1996-05-29 | 1997-12-09 | Sumitomo Chem Co Ltd | カチオン染料によるセルロース系繊維の染色又は捺染方法 |
| WO2000036211A1 (en) | 1998-12-17 | 2000-06-22 | Clariant Finance (Bvi) Limited | Dyeing process and dye composition |
| WO2004012406A1 (en) | 2002-07-29 | 2004-02-05 | Research In Motion Limited | System and method of mimetic messaging settings selection |
| WO2005012437A1 (en) | 2003-07-24 | 2005-02-10 | Ciba Specialty Chemicals Holding Inc. | Cationic direct dyes |
| US20060059635A1 (en) | 2004-02-18 | 2006-03-23 | Melvin Alpert | Method for dyeing fabric materials with indigo, other vat dyes, and sulfur dyes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113550047A (zh) * | 2021-08-18 | 2021-10-26 | 浙江美欣达纺织印染科技有限公司 | 仿靛蓝牛仔面料及生产方法 |
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