WO2012064859A2 - Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet - Google Patents
Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet Download PDFInfo
- Publication number
- WO2012064859A2 WO2012064859A2 PCT/US2011/059997 US2011059997W WO2012064859A2 WO 2012064859 A2 WO2012064859 A2 WO 2012064859A2 US 2011059997 W US2011059997 W US 2011059997W WO 2012064859 A2 WO2012064859 A2 WO 2012064859A2
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- Prior art keywords
- fiber
- aqueous dispersion
- composition
- sulfate
- nitrate
- Prior art date
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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
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
Definitions
- This disclosure relates to the carpet industry in general and to the application of carpet dyeing and finishing chemistry in particular.
- the disclosed aqueous dispersion of dye, stain-blocker, and fluorochemical and application thereof relates especially to the treatment of carpet fiber to maintain carpet appearance after extended use.
- the aqueous dispersion and processes disclosed herein provide superior appearance retention via stain and soil protection while using far less water and energy than processes of the prior art.
- the aqueous dispersion and processes are applicable to various fibers, including nylon 6,6 and copolymers and blends thereof.
- the invention disclosed herein provides a stable aqueous dispersion of dye, stain-blocker, and fluorochemical that can be applied as a composition to fibers for carpets and fabrics.
- Such solution overcomes the problem of dyes reacting too quickly at low pH, by adjusting the conductivity of the solution to a level where the dyes can react at a pace that provides uniform color throughout.
- the composition pH can remain relatively low for stain and soil resist chemistry to be effectively applied.
- processes for applying the aqueous dispersion and carpets and fabrics made with the fibers treated with the composition and aqueous dispersion are also disclosed.
- a composition comprising an aqueous dispersion of a dye, an anti- soil component, and a stain blocker component.
- the aqueous dispersion has a conductivity between about 2000 to about 9000 micromhos, and a pH between about 1.5 to about 5.
- the anti-stain component can comprise a fluorochemical.
- aqueous dispersion can comprise a metal salt and / or a retarder.
- a method of applying the composition to a fiber comprises: (a) providing an aqueous dispersion comprising a dye, an anti- soil component, and a stain blocker, wherein said aqueous dispersion has a
- the fiber can be manufactured into a carpet or fabric.
- a pre-treated fiber can be manufactured into a carpet or fabric, and then the carpet or fabric treated with the composition as disclosed above.
- the fiber can be any type, including natural staple, synthetic staple, or synthetic continuous filament.
- the contacting can be done using known processes, such as bathing, exhaustion, foaming, spraying, and nip-rolling, and can also be implemented as part of various dyeing processes such as skein dyeing, beck dyeing, piece dyeing, and space dyeing.
- a composition comprising an aqueous dispersion of a dye, stain blocker, and a retarder.
- the retarder reacts with dye sites and competes for the fiber surface along with the dye, thus reducing the rate of dyeing and creating more level dyeing.
- the composition can further comprise an anti-soil component to make a four-part composition.
- a method of applying a composition to a fiber is disclosed.
- Such method comprises: (a) providing an aqueous dispersion comprising a dye and a stain blocker, wherein said aqueous dispersion has a conductivity between about 2000 to about 9000 micromhos and a pH between about 1.5 to about 5; (b) contacting said fiber with said aqueous dispersion at temperature between about 20°C to about 40°C; (c) steaming said fiber for at least 60 seconds; (d) rinsing said fiber with water; and (e) drying said fiber.
- the water can be removed from the fiber prior to drying.
- This method can be used with fibers that are already treated with an anti-soil component, that have inherent anti-soil properties, or will be post-treated with an anti- soil component after contacting with the aqueous dispersion.
- a carpet fiber comprising a dye, an anti-soil component, and a stain block is disclosed.
- the stain block penetrates farther into said fiber than the stain block applied separately from a dyeing step.
- Figure 1 depicts a known process of applying a dye, stain blocker, and anti-soil component in three separate steps.
- Figure 2 depicts on aspect of the disclosed method of applying a composition comprising dye, stain blocker, and anti-soil components.
- QWF On weight of fiber
- WPU Weight pick-up
- a composition comprising an aqueous dispersion of a dye, an anti-stain component, and a stain blocker is disclosed.
- the aqueous dispersion is buffered to a pH of between about 1.5 to about 5, including about 2 to about 4, and about 3 to about 5.
- the conductivity of the aqueous dispersion is also adjusted from about 2000 to about 9000 micromhos, including from about 4000 to about 9000 micromhos, from about 2000 to about 7000 micromhos, and from about 4000 to about 7000 micromhos.
- the disclosed composition can use a variety of stain blockers, such as syntans, sulfonated novolacs, or sulfonated aromatic aldehyde condensation products (SACs).
- Stain blockers are usually made by reacting formaldehyde, phenol, polymethacrylic acid, maleic anyhydride, and sulfonic acid depending on specific chemistry.
- anti-soil components can be used in the composition, including fluorochemical and non-fluorochemical based.
- the fluorochemicals can be anionic or cationic or contain extenders (See e.g. U.S. Patent No. 5,756,407 herein incorporated by reference in its entirety).
- stain blockers examples include: formaldehyde polymers or copolymers, such as CEASESTAIN and STAINAWAY (from American Emulsions Company, Inc., Dalton,
- MESITOL from Bayer Corporation, Rock Hill, N.C.
- ERIONAL from Ciba
- LANOSTAIN from Lenmar Chemical Corporation, Dalton, Ga.
- SR-300; SR-400; and SR-500 from DuPont, Wilmington Del.
- polymers of methacrylic acid such as the SCOTCHGUARD FX series (from 3M Company, St. Paul Minn.); and sulfonated fatty acids from Rockland React-Rite, Inc.; stain resist chemistries from ArrowStar LLC,
- fluorochemical anti-soil components include: fluorochemical emulsions, such as AMGUARD (from American Emulsions Company); SOFTECH (from Dyetech); LANAPOL (from Lenmar Chemical Corporation); SOCTCHGUARD FC (from AMGUARD (from American Emulsions Company); SOFTECH (from Dyetech); LANAPOL (from Lenmar Chemical Corporation); SOCTCHGUARD FC (from AMGUARD).
- AMGUARD from American Emulsions Company
- SOFTECH from Dyetech
- LANAPOL from Lenmar Chemical Corporation
- SOCTCHGUARD FC from SOCTCHGUARD FC
- NK GUARD from Nicca USA, Inc., Fountain Head, N.C.
- UNIDYNE from Diakin
- the aqueous dispersion or composition can optionally contain a metal salt in a range from about 1 gram of metal / Liter to about 16 gram of metal / Liter of aqueous solution, including from about 1 gram of metal / Liter to about 6 gram of metal / Liter of said aqueous solution.
- metal salts include: sodium sulfate, magnesium sulfate, potassium sulfate, calcium sulfate, manganese sulfate, iron sulfate, copper sulfate, zinc sulfate, aluminum sulfate, sodium nitrate, magnesium nitrate, potassium nitrate, calcium nitrate, manganese nitrate, iron nitrate, copper nitrate, zinc nitrate, aluminum nitrate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, manganese chloride, copper chloride, iron chloride, sodium phosphate, potassium phosphate, calcium phosphate, manganese phosphate, iron phosphate, copper phosphate, zinc phosphate, aluminum phosphate, sodium bicarbonate, sodium carbonate, calcium bicarbonate, calcium carbonate, potassium bicarbonate, and potassium carbonate.
- a retarder can be used in the aqueous dispersion or composition in a range from about 0.25% to about 4% by weight aqueous solution, including 0.5% to about 2% by weight of aqueous solution.
- An example retarder is DOWFAX 2A4 or DOWFAX 2A1. The retarder competes for the fiber surface along with the dye, thus reducing the rate of dyeing and creating more level dyeing.
- an aqueous dispersion comprising a dye, stain blocker, and retarder is disclosed.
- compositions can be used with fibers that are already treated with an anti-soil component, that have inherent anti-soil properties, or will be post-treated with an anti- soil component after contacting with the aqueous dispersion.
- the retarder can adjust the conductivity of the aqueous dispersion from about 2000 to about 9000 micromhos, including from about 4000 to about 9000 micromhos, from about 2000 to about 7000 micromhos, and from about 4000 to about 7000 micromhos.
- compositions can also contain additives to aid in dye penetration, anti-soil penetration, stain blocker penetration, as well as additives to protect the carpet from long term exposure to the elements and additives to keep the three components in suspension.
- additives include: dye auxiliaries, sequestrants, pH control agents, surfactants, fluoro-surfactants, nano materials, odor control agents, antimicrobial agents, fragrance agents, bleach resist agents, softeners, and UV stabilizers.
- the rate of dye reaction is retarded so that uniformity can be obtained.
- dye application is at 5-6 pH, and the conductivity is not high (i.e. 265 micromhos).
- the conductivity is not high (i.e. 265 micromhos).
- the process comprises contacting the fiber with the aqueous dispersion at a temperature between about 20°C to about 40°C, including between about 24°C to about 28°C.
- the fiber is steamed for at least 60 seconds, including from about 2 to about 3 minutes, followed by rinsing and drying the fiber. Water can be removed from the fiber prior to drying using conventional methods, such as suction, nip-rolling, centrifuge, and convection.
- the steaming cycle to fix dye and stain blocker will be at a steam temperature close to 100°C and the drying can be performed at a temperature between about 130-135°C. It should be noted that the temperatures will be dependent on the line speed, and specific type of equipment used.
- the fiber can be pre-heated or steamed prior to contacting the fiber with the aqueous solution.
- the fiber can be any type, including natural staple, synthetic staple, or synthetic filament.
- Natural staple fibers include wool.
- Synthetic fibers include polyamide, polyester, and polyolefin. Examples of polyamides include: nylon 6,6, nylon 6, nylon 4,6, nylon 6,10, nylon 10,10, nylon 12, its copolymers, and blends thereof. Polyamide copolymers can also include 5-sulfosiophthalic acid, methylpentamethylenediamine, and isophthalic acid moieties.
- the fiber can be manufactured into various articles, including carpets and fabrics either before or after contacting said fiber with the aqueous solution.
- the disclosed processes can be applied to the fiber prior to forming the article or after forming the article.
- the process can further comprise, prior to contacting the fiber with the aqueous dispersion, steam heat setting the fiber at a temperature between about 118°C to 145°C or optionally a dry heat set at a temperature between about 145°C to 205°C.
- the optional dry heat set provides additional stain resistance.
- the stain blockers have a range of molecular size and it is theorized that the stain blocker during the steam fixation step migrates to the interior.
- the extent of migration depends on the steaming conditions and the molecular size of the stain blocker.
- the durability of stain resistance to detergent washing, for example, will depend on how much of the stain blocker is left on the surface verses how much has penetrated the surface.
- the steam fixing step after dyeing is usually longer and using this step for steam fixing will more effectively drive the stain blocker into the fiber and provide more durability compared to traditional steam fixing post-stain blocker application.
- suitable design of molecular sizes one can ensure more of the stain blocker stays on the surface and less penetrates the surface.
- Such modification of molecular sizes and types of stain blockers to further enhance the tri-application process is contemplated by this disclosure.
- one of skill in the art can design a mixture of molecular sizes for the stain blocker, that will ensure some larger molecules stay on the surface and smaller molecules penetrate, thereby offering not only improved initial stain resistance but also durability of stain resistance.
- the longer steam fixing step provides for more durability of anti-soil chemistries, since anti-soil components are typically non-water soluable.
- a method of applying a composition to a fiber where the composition comprises an aqueous dispersion comprising a dye and a stain blocker.
- the aqueous dispersion is kept at a conductivity between about 2000 to about 9000 micromhos, including from about 4000 to about 9000 micromhos, and about 4000 to about 7000 micromhos; and a pH from about 1.5 to about 5, including about 2 to about 4 and about 3 to about 5.
- the fiber is contacted with the aqueous solution, followed by steaming, rinsing, drying, and optionally removing the water prior to drying.
- an anti-soil component as discussed above, can be applied after contacting the fiber with the aqueous solution.
- the anti-soil component can be applied using numerous methods, such as spraying or foaming.
- the fiber can be manufactured into an article before or after contacting the fiber with the aqueous solution.
- This method is especially applicable to those fibers that have inherent anti-soil characteristics or in processes where the specific anti-soil is most effectively applied by foaming of spraying. Further, in some applications, the application of an anti-soil component, such as a fluorochemical, may not be necessary or desired. Such applications include non-allergen fabrics and certain eco-friendly fabrics.
- the disclosed processes effectively eliminates several steps from the known fiber, carpet, and fabric treatment processes, including multiple rinsing, washing, and steaming steps.
- the process is surprisingly effective in that intermediately low pH levels have been found effective for application of certain stain resist chemistries when applied in the presence of acid dyes, while certain combinations of stain and soil resist chemistry were found to be surprisingly effective in moderating acid dye rate, so that dyed fabrics were surprisingly uniform.
- Figure 1 depicts a known process of applying a dye, stain blocker, and anti-soil component in three separate steps to a carpet. The carpet is fed to pre-steamer 5, where it is pre-steamed prior to entering the dyer 10.
- the carpet is fed to main steamer 15, rinsed 20, and water is extracted in the extractor 25.
- Stain-block is applied in a flex-nip applicator 30, followed by post-steaming 35.
- the carpet is then washed 40 and the water extracted 45.
- anti-soil is applied via a spray applicator 50 and the carpet dried 55.
- Figure 2 depicts one aspect of the disclosed process as applied to a carpet.
- the carpet is fed to a pre-steamer 105, where it is pre-steamed prior to applying the disclosed composition 1 10.
- the carpet is fed to a main steamer 15, rinsed 120, and the water is extracted in the extractor 125. Finally, the carpet is dried 130. Because the anti-soil component and stain blocker go through a much longer steam fixing cycle than known processes, the surface texture of the carpet fiber will differ and the stain blocker penetrates deeper into the carpet fiber.
- compositions and methods are beneficial to almost any fabric treatment process where dyes, stain blockers, and anti-soil components are employed, especially where dye and stain resist can be placed in competition with one another for amine ends (i.e. acid dye sites) in the dye bath.
- Articles to which the disclosed compositions and methods are applicable include: textile fabrics, rugs, carpets, furniture coverings, automotive upholstery, draperies, and various other soft surfaces to which dyes and stain blocking chemistries are both applied.
- nylon carpets treated with various aspects of the disclosed compositions compared to standard treatments with separate components.
- Selection of alternative anti-soil components, dyes, stain blockers, fibers, and textiles having different surface chemistries will necessitate minor adjustments to the variables herein described.
- Conductivity measurement Conductivity measurements were taken with a Myron L Co. Ultrameter II model 6Psi. Samples including two Myron L KCI conductivity standards (700 and 7000micromhos) were heated to approximately 25°C in a laboratory oven. The conductivity instrument cell was rinsed 3 times with sample solution before taking sample measurements. Three replications of each sample was measured and recorded when the temperature range was at 24.9 - 25.2°C.
- a control carpet sample was prepared as follows: Two 995 denier nylon 6,6 yarns (Fiber 995-476AS, a mild dull, medium acid dyeable, fiber with wavy trilobal cross section available from INVISTA) were twisted to 6 twists-per-inch and heat set via a Superba heat set process at a temperature of 265°F with residence time of 28 seconds and tufted into 1/8" gage, 9/16" pile height carpet with a weight of 45-46 ounces / square yard. The carpet was then dyed using the dye mixture below to a wool beige color. Stain blocker and anti-soil were not added. The control carpet had an initial stain rating of 1 , a stain rating of 1 after 1 WAQE wash and a stain rating of 1 after 3 WAQE washes.
- Sample carpets were prepared similar to above, except that a Suessen heat set at 195°C, instead of Superba heat set, was performed on the yarn for 60 seconds residence time.
- a tri-component composition was prepared as follows: A mixture of dyes (Yellow 3G, Red 2B, and Blue 4R to obtain a wool beige color), stain blocker (s-801 from INVISTA) at 4%, and anti-soil (Capstone RCP fluorochemical) at a concentration that imparts a final fluorine OWF between 150-250 ppm was prepared at room temperature. Also added to the mixture was a 40% wt/wt aqueous magnesium salt mixture (10 grams of metal / liter) to adjust the pH to about 2.1.
- Table 1 below shows the results of applying dye, stain blocker (SB), and anti-soil using the traditional method (Sample 1), and two aspects of the disclosed process using the tri-component composition described above. (Samples 2 and 3). The composition was applied at 80°F.
- Sample carpets were prepared as discussed above, except that the yarn was heat set in a Superba heat setting machine at 265°F , with a residence time of 28 seconds.
- the carpet was treated on a range continuous dyer as described in Table 2 below.
- the dye was the wool beige color described above.
- the carpets were tested for stain resistance.
- the tri-component composition was prepared as above without the salt, with the variations disclosed in Table 2.
- the stain blocker in all cases was S-801 at 4.0% and 2.1pH, unless otherwise stated.
- Samples 8 and 9 used MgS0 4 in the concentrations disclosed above.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2011800644520A CN103282577A (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersion of dye, stain-locker, and fluorochemical and its use in the manufacture of carpet |
EP11839346.1A EP2638204A2 (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
NZ610055A NZ610055A (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
US13/884,701 US20140033451A1 (en) | 2010-10-19 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
JP2013538857A JP2014501806A (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersions of dyes, stain blockers and fluorochemicals and their use in the manufacture of carpets |
CA2817009A CA2817009A1 (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
AU2011326497A AU2011326497A1 (en) | 2010-11-12 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US41306610P | 2010-11-12 | 2010-11-12 | |
US61/413,066 | 2010-11-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2012064859A2 true WO2012064859A2 (en) | 2012-05-18 |
WO2012064859A3 WO2012064859A3 (en) | 2012-07-19 |
Family
ID=46051538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/059997 WO2012064859A2 (en) | 2010-10-19 | 2011-11-09 | Aqueous dispersion of dye, stain-blocker, and fluorochemical and its use in the manufacture of carpet |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP2638204A2 (en) |
JP (1) | JP2014501806A (en) |
CN (1) | CN103282577A (en) |
AU (1) | AU2011326497A1 (en) |
CA (1) | CA2817009A1 (en) |
NZ (1) | NZ610055A (en) |
WO (1) | WO2012064859A2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103898775A (en) * | 2014-04-18 | 2014-07-02 | 长兴宏峰纺织印染有限公司 | Fabric cleaning, printing and dyeing process |
CN103938471A (en) * | 2014-04-18 | 2014-07-23 | 长兴宏峰纺织印染有限公司 | Printing and dyeing process of cotton fabric |
CN104499307A (en) * | 2014-12-18 | 2015-04-08 | 太湖亚太精化有限公司 | Dispersing type dye with high dyeing fastness, and preparation method thereof |
CN104530758A (en) * | 2014-12-18 | 2015-04-22 | 太湖亚太精化有限公司 | Heterocyclic disperse dye and preparation method thereof |
EP2904139A4 (en) * | 2012-09-19 | 2016-06-15 | INVISTA Technologies S à r l | Apparatus and method for applying colors and performance chemicals on carpet yarns |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2944196A1 (en) * | 2014-04-09 | 2015-10-15 | Invista Technologies S.A R.L. | Water repellent, soil resistant, fluorine-free compositions |
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2011
- 2011-11-09 CA CA2817009A patent/CA2817009A1/en not_active Abandoned
- 2011-11-09 EP EP11839346.1A patent/EP2638204A2/en not_active Withdrawn
- 2011-11-09 CN CN2011800644520A patent/CN103282577A/en active Pending
- 2011-11-09 AU AU2011326497A patent/AU2011326497A1/en not_active Abandoned
- 2011-11-09 WO PCT/US2011/059997 patent/WO2012064859A2/en active Application Filing
- 2011-11-09 NZ NZ610055A patent/NZ610055A/en not_active IP Right Cessation
- 2011-11-09 JP JP2013538857A patent/JP2014501806A/en active Pending
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2904139A4 (en) * | 2012-09-19 | 2016-06-15 | INVISTA Technologies S à r l | Apparatus and method for applying colors and performance chemicals on carpet yarns |
CN103898775A (en) * | 2014-04-18 | 2014-07-02 | 长兴宏峰纺织印染有限公司 | Fabric cleaning, printing and dyeing process |
CN103938471A (en) * | 2014-04-18 | 2014-07-23 | 长兴宏峰纺织印染有限公司 | Printing and dyeing process of cotton fabric |
CN103938471B (en) * | 2014-04-18 | 2015-11-04 | 长兴宏峰纺织印染有限公司 | A kind of dyeing and printing process of COTTON FABRIC |
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CN104499307A (en) * | 2014-12-18 | 2015-04-08 | 太湖亚太精化有限公司 | Dispersing type dye with high dyeing fastness, and preparation method thereof |
CN104530758A (en) * | 2014-12-18 | 2015-04-22 | 太湖亚太精化有限公司 | Heterocyclic disperse dye and preparation method thereof |
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CN103282577A (en) | 2013-09-04 |
AU2011326497A1 (en) | 2013-05-23 |
JP2014501806A (en) | 2014-01-23 |
NZ610055A (en) | 2015-09-25 |
EP2638204A2 (en) | 2013-09-18 |
CA2817009A1 (en) | 2012-05-18 |
WO2012064859A3 (en) | 2012-07-19 |
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