WO1992015750A1 - Procede de teinture de substrats en polyamide - Google Patents

Procede de teinture de substrats en polyamide Download PDF

Info

Publication number
WO1992015750A1
WO1992015750A1 PCT/US1992/001866 US9201866W WO9215750A1 WO 1992015750 A1 WO1992015750 A1 WO 1992015750A1 US 9201866 W US9201866 W US 9201866W WO 9215750 A1 WO9215750 A1 WO 9215750A1
Authority
WO
WIPO (PCT)
Prior art keywords
vinyl sulfone
dye
dyes
dyed
substrate
Prior art date
Application number
PCT/US1992/001866
Other languages
English (en)
Inventor
Larry C. Kelley
Original Assignee
Hoechst Celanese Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corporation filed Critical Hoechst Celanese Corporation
Publication of WO1992015750A1 publication Critical patent/WO1992015750A1/fr

Links

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
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/248—Polyamides; Polyurethanes using reactive dyes

Definitions

  • This invention is directed to the dyeing of polyamide fibers.
  • the dyeing of natural fibers to impart color and styling effects to textile substrates can be traced back to the earliest dates of recorded history.
  • a multitude of natural and synthetic dyes have been developed to accomplish such effects over the years and have been applied to synthetic fibers.
  • One important class of such synthetic dyes are the fiber reactive dyes containing the vinyl sulfone substituent or its chemically reactive analog e.g. the sulfatoethyl sulfonyl substituent.
  • These fiber reactive dyes, hereinafter called vinyl sulfone dyes are capable of forming covalent bonds between the dye molecule and the textile substrate.
  • vinyl sulfone dyes are described in the patent, literature as being useful in dyeing practically all known natural and synthetic textile substrates. However, the main commercial application of such dyes has been in the dyeing of cotton. Since the early 1950's, it has been taught that vinyl sulfone type and other reactive dyes can dye wool and nylon to provide high wash and wet fastness properties see e.g. U.S. Patent No. 3,223,470 to Boedeker et al.
  • U.S. Patent 3,118,723 discloses dyeing nylon with dyestuffs containing at least 2 sulfonic acid groups and 0 to 3 reactive groups (vinyl sulfone or cyanuric chloride groups) in the presence of a condensation product of an "aldone” (aldehydic or ketonic carbonyl compound) and an aryl sulfonic acid to produce a random multi-colored dyeing.
  • the author reports an earlier process for using vinyl sulfone dyes in the coloring of polyamides.
  • the substrate is introduced into an acidic, aqueous bath to which a previnylized vinyl sulfone dye is added. After holding the acidic bath for a predetermined time, the substrate is treated in an alkaline bath.
  • the review author reports that unlevel dyeing result from this process.
  • fiber reactive vinyl sulfone dyes have not been widely used in dyeing wool and synthetic polyamides because they lack substantivity at high pH values (i.e. 7 or above) where their maximum reactivity is present and because they tend to produce unlevel dyeings at such pH values.
  • vinyl sulfone dyes (Hostalan ® Dyes) are recommended for use on wool and nylon in straight shades (monochromatic dyeing) or in heavy shades. It is also generally recommended that such dyeings be given a short afterwash with ammonia to improve their wash fastness by stripping unfixed dye.
  • This invention is directed to the use of vinyl sulfone dyes in the dyeing of polyamides, particularly in multicolored nylon dyeings.
  • the invention provides a process for producing level polyamide dyeing having superior fastness and overdye properties.
  • This invention comprises a method for dyeing polyamide fibers using vinyl sulfone fiber reactive dyes. Dyeings having superior wet fastness, overdye fastness and laundry fastness properties are obtained.
  • the process of the invention may be used to dye natural and synthetic polyamide substrates in the form of fibers such as yarn, stock, knit, carpet or other fabric substrates by either exhaust or continuous dyeing processes.
  • the essential elements of the invention comprise contacting the polyamide substrate with at least one vinyl sulfone dye in an aqueous medium at an acidic pH from about 1.5 to about 5.
  • the dyeing is held at this acidic pH for an effective amount of time and temperature to allow the vinyl sulfone dye to migrate into the polyamide substrate; e.g. using an exhaust process, 15 minutes at the boil.
  • the pH of the dyeing is then raised to about 8 to about 12 by the addition of base and heated for an effective amount of time and temperature to covalently bond the vinyl sulfone dye to the polyamide substrate; e.g. using an exhaust process 30-45 minutes at the boil.
  • the vinyl sulfone fiber reactive dyes useful in the invention are known in the textile art. They may be represented by the general formula: (SO 3 M) m -D-(SO 2 -Z) n wherein "M” represents hydrogen and water soluble metal atoms, "D” represents a dye chromophore, "Z” represents a fiber reactive moiety and "m” and "n” represent integers of 1-4 and 1-3 respectively.
  • M represents hydrogen and water soluble metal atoms
  • D represents a dye chromophore
  • Z represents a fiber reactive moiety and "m” and "n” represent integers of 1-4 and 1-3 respectively.
  • one of the moieties-(SO 2 -Z) may be replaced by another fiber reactive group such as a mono- or di-halogen-s-triazine.
  • the covalently bonded dye chromophore produces a dyed polyamide substrate with superior wet fastness, laundry fastness and overdye fastness.
  • Dyeings of the invention may be treated with an anionic resist compound such as the condensation polymer of formaldehyde and an aryl sulfonic acid or salt thereof to prevent stripping and redeposition of the vinyl sulfone dye in subsequent overdyeing or laundering operations.
  • Illustrative applications of the invention are dyed entrance carpets which must withstand repeated exposures to water and repeated laundering.
  • yarn dyed according to the invention may be tufted into carpeting with griege yarn and overdyed to achieve a multitude of stylized color effects.
  • a substrate may be printed with a pattern of at least one vinyl sulfone dye under acid conditions, treated with base and heat to covalently fix the dye and then overdyed with a standard acid dye such as a level dyeing monosulfonated acid dye to produce a multi-colored polyamide substrate.
  • This invention is a process for dyeing polyamides to provide superior wet fastness, wash fastness and overdye properties.
  • Polyamides useful in the practice of the invention include both the natural and synthetic fiber- forming polyamides. Examples of such polyamides are wool, silk, nylon-6, nylon-6,6, nylon-11, nylon-12, nylon-6/6,6, nylon-6, 12 etc. Particularly preferred polyamides are wool, nylon-6, nylon-6,6 and nylon 6/6,6 copolymers and blends of such synthetic polyamides. The invention is most particularly useful in dyeing of nylon-6 and nylon-6,6.
  • Polyamide substrates dyed in accordance with the invention may be combined with other polyamide substrates or other substrates such as polyurethane, polypropylene, polyethylene, polyester, rayon, wool, silk, etc.
  • the process of the invention may be used to dye polyamide substrates in the form of yarns, fibers, knit goods, fabric, stock, carpets etc. Additionally, the process of the invention may be practiced by exhaust and continuous dyeing methods.
  • the process of the invention comprises:
  • the dyed polyamide may be optionally treated with an anionic, water soluble, fiber-substantive resist chemical in about 1 to about 5 percent (owf - on weight of fiber) to provide a dyed polyamide substrate having superior wet and wash fastness properties as well as superior overdye properties.
  • Overdyeing as used in this description means that a subsequent dyeing is effected after the vinyl sulfone dyed polyamide is incorporated into another article; e.g. vinyl sulfone dyed polyamide yarn is tufted into a carpet with griege yarn which is then dyed.
  • the vinyl sulfone dyed substrates made in accordance with the invention exhibit superior resistance to stripping and redeposition on the griege yarn.
  • the fiber-reactive, vinyl sulfone type dyes useful in the practice of the invention are known.
  • the main use of such fiber-reactive, vinyl sulfone type dyes has been in the dyeing of cotton.
  • U.S. Patent No. 3,802,837 and 4,762,524 teach their use in the dyeing of polyamides.
  • These prior art references teach to use the vinyl sulfone dye as a reaction product with a substituted, secondary aliphatic amine such as n-methyltaurine.
  • Suitable dyes of the vinyl sulfone type are represented by the following general formula:
  • D represents a dye chromophore selected from the anthraquinone, dioxazine, formazon, phthalocyanine, mono- and disazo series and their metal complexes wherein the metal is selected from copper, chromium, iron, cobalt and nickel; preferably copper or nickel. Particularly preferred are those chromophores of the formazon series, the mono- and disazo series and their metal complexes.
  • Z represents the fiber reactive group: -CH 2 -CH 2 -Y wherein "Y” is a substituent capable of being split off by an alkaline reagent: e.g., chlorine, bromine, thiosulfate, sulfato, phosphato, a carboxylic acyloxy of one to four carbon; or by an acidic reagent: e.g., dimethylamino, diethylamino, N-alkyl (C 1 to C 4 ) acids.
  • the sulfato group is most preferred.
  • the term "n” represents an integer from 1 to 3; preferably 2-3 and most preferably 2.
  • the term "m” represents an integer from 1 to 4, preferably 1 to 3 and most preferably l to 2.
  • the term "M" represents hydrogen and the water soluble metals; e.g. sodium, potassium, lithium or calcium; preferably sodium.
  • the dye chromophore may contain in addition to the vinyl sulfone group an additional fiber reactive groups: e.g. a mono- or di-halogen-s-triazine, a mono cyanamido-s-triazine, a mono-, di- or tri- halogen pyrimidine, a mono or dichloroquinoxaline, a dichlorophthalazine, a dichloropyridazone or the bromine or fluorine derivatives thereof.
  • the vinyl sulfone dyes may be employed in their water soluble salt form e.g.
  • vinyl sulfone dyes are termed mixed anchor dyes: i.e. a vinyl sulfone group and a mono-, or di-halogen-s-triazine group .
  • vinyl sulfone dyes can be effectively used in the practice of the invention. It has been found that the number of solubilizing groups does not appear to have a significant affect in the process beyond the normal wet fastness, solubility and substantivity properties that a comparable acid dye would have. In continuous dyeing processes, a vinyl sulfone dye having at least two fiber reactive groups perform best. In continuous dyeing processes, dyes with a single fiber reactive group provides improved wet fastness but they do not appear to be particularly suited to use in the continuous processes.
  • a vinyl sulfone dye having only one fiber reactive group will work in the process of the invention.
  • fiber reactive, vinyl sulfone dyes with at least two fiber reactive groups are still preferred.
  • the preferred fiber reactive vinyl sulfone dyes useful in the invention are those with two or more fiber reactive groups, e.g. two vinyl sulfone groups (-SO 2 -Z), a vinyl sulfone and a monochloro-s-triazine or two vinyl sulfone groups and a monochlorotriazine group etc. Additional illustrative fiber reactive groups are the triazine, pyrimide, haloquinoxaline, or halophthalazine types previously described; most preferred are the monochloro-s-triazines.
  • the selection of the vinyl sulfone dye or dyes may be determined by simple experimentation within the above parameters.
  • auxiliary agents such as ethoxylated aliphatic amines; may be added to the dye mixture to compatibilize the strike rates of the dyes.
  • Various cationic leveling agents can be employed depending on the dyeing conditions. The amounts used can be from 2.0 to 6.0 g/l of a 30% active tallow amine with 15 moles of ethylene oxide, or a 30% active tallow diamine with 105 moles ethylene oxide, or a tallow diamine with 28 moles ethylene oxide that has been quaternized.
  • Sequesterants such as ethylenediamine tetra-acetic acid and nitrilotriacetic acid should not be used.
  • no auxiliary chemicals other than water or steam
  • an alkaline reagent such as trisodium phosphate.
  • the application pH should be between 1.5 - 4.0, with 2.0 to 2.5 being preferred.
  • Sulfamic acid 1-4 g/l
  • acid buffers give inconsistent results.
  • the pH should be between 8-12.
  • Alkaline reagents useful in the practice of the invention are well known in the art. They are those substances capable of converting the sulfonyl moiety to its fiber reactive form, i.e.
  • Alkali metal salts and hydroxide such as trisodium phosphate or soda ash or potassium phosphate, potash ash, caustic etc. can be used in amounts between 10 - 50 g/l. ammonia is not useful for this purpose. IT is known in the art that ammonia will strip an unfixed vinyl sulfone dye from the textile substrate. In exhaust dyeing situations, the dyebath containing vinyl sulfone dyes should be at pH 3.0 - 5.0 at the beginning of the cycle and held there until the bath has reached the boil for 15 minutes. At this point the pH is raised to the alkaline side and the bath is boiled an additional 30-45 minutes.
  • the vinyl sulfone dye In continuous or print applications, the vinyl sulfone dye should be steamed on the acid side for 6 - 10 minutes and on the alkaline side for 4 - 8 min.
  • the dyed substrate For good results using thermofixing methods, the dyed substrate must be above 300°F for 30 seconds to 30 minutes.
  • fixing may be achieved using saturated steam at temperatures as low as 270°F with dwell times as little as 45-65 seconds when the substrate used is yarn.
  • the proper time and temperature to effect fixation of the vinyl sulfone dye by covalent bonding will depend on the process (exhaust or continuous), the equipment employed and the amount of moisture present.
  • the vinyl sulfone dye is applied by continuous means (padding, printing, flooding, spraying etc.) at low pH and then steamed for about 5 - 8 minutes, preferably about 6 minutes.
  • the vinyl sulfone dyed polyamide is washed and then passed through a washbox containing an alkaline solution.
  • the substrate is then dried with heat and partial covalent bonding occurs.
  • the substrate can be then given an additional heat treatment to complete the covalent fixing process.
  • subsequent twist-heat setting operations such as autoclaving, Suessen setting or Superba setting will thermofix the dye giving almost complete covalent bonding.
  • Superba setting accomplishes thermofixing with saturated steam at temperatures as low as 270°F and dwell times between 45-65 seconds.
  • Suessen thermofixing uses dry heat at temperatures above 390°F and dwell times of 55-65 seconds.
  • Autoclaving although technically a batch process, uses saturated steam at a temperature up to 280°F using alternating cycles of 12-18 minutes. Alternatively after the alkali is applied the substrate may be simply steamed for 6 - 8 minutes.
  • a third variation is to give the substrate a short steaming cycle after alkali application and dried in the normal manner. The dried substrate can then be heated to 300 - 340°F for 15 - 20 minutes to complete the fixing step; e.g. when a washable rug is made, the dyed carpet is bonded to a rubber or vinyl backing at 320°F for 15 - 20 minutes.
  • the normal dyebath chemicals employed in dyeing monosulfonated acid dyes can be used such as sodium dodecyl diphenyloxide disulfonate. If there is some unreacted vinyl sulfone dyes present during an overdye cycle, the addition of 1 - 5 % owf of a anionic chemical will prevent stripping and redeposition on the greige resist carpet and the same also holds true in laundering operations.
  • anionic resist is not readily explained since they are normally applied at pH's of 2.0 - 4.5 and in the above cases the bath pH's are between about 6.0 and about 10.0., e.g. acid dyes are normally applied from about pH 6.0 to about 7.5 and in laundering the pH is normally between about 7.0 to about 10.0.
  • the anionic, water-soluble, fiber-substantive resist chemicals useful in the invention include sulfonated phenol-aldehyde condensation products, a sulfonated naphthol condensation product, polymethacrylic acid polymers, acrylic acid polymers, copolymers of acrylic acid or methacrylic acid with ethylenically unsaturated comonomers, the polymerization reaction product of an alpha-substituted acrylic acid or ester prepared in the presence of one of the above described sulfonation condensation products, the water soluble salts of said condensation products and said polymerization products and mixtures thereof.
  • the anionic, water-soluble, fiber substantive resist chemical useful in the invention contain -SO 3 X and - COOX substituents wherein X is hydrogen or a cation of the alkali earth metals e.g. sodium, potassium, lithium, or an ammonium ion.
  • the resist chemicals useful in this invention are characterized in that they may be applied in combination with an acid or direct dye and the acid or direct dye may be fixed to the fiber area.
  • anionic resist chemicals prepared by polymerizing an alpha substituted acrylic acid or ester in the presence of a sulfonated aromatic - aldehyde condensation polymer is described in U.S. Patent 4,940,757 at Column 3-6 thereof and the Examples of said patent; the teachings thereof are hereby incorporated by reference.
  • Illustrative commercially available anionic resist are Erional ® PA and Erional ® NW from Ciba Geigy; Intratex ® N from Crompton and Knowles, Stainfree ® from Sybron and Karafix ® NA from Lyndal. These resists are sulfonated condensation products of aldehydes and phenols or naphthols and they are the preferred type of anionic resist chemical for the practice of the invention.
  • Another anionic resist commercially available is 3M Company's stainblocker FX 661, a mixed sulfonated condensation product of a phenol and aldehyde with a methacrylic polymer.
  • Leukotan ® 970, 1027, 1028 and QR 1083 from Rohm and Haas Co. are examples of commercially available methacrylic polymer anionic resist chemicals. These chemicals are used presently in the textile dyeing industry as stainblockers, leveling agents and wet fastness additives.
  • the acid dyes which can be used in this invention to overdye substrates containing vinyl sulfone dyed substrate are those dyes containing one or more anionic functional groups.
  • the acid dyes useful in the practice of the invention are classified in the "Color Index” under the classifications “Acid” and “Direct”. "Mordant” dyes and “Reactive” dyes under the “Color Index” classification are not within the scope of the term acid dyes as used in this disclosure, nor are those dyes having fiber reactive substituents. Acid dyes have large molecules containing one or more functional sulfonic or carboxylic acid salt groups.
  • Direct dyes are a special class of dyes which have a long, narrow, flat molecule and one or more carboxylic or sulfonic acid salt functional groups which allow these dyes to function in the same manner as an "Acid” dyes.
  • the "acid” dyes useful in the invention are termed "anionic dyes" in U.S. Patent 4,218,217 and described at Column 4, lines 29-59 thereof; the disclosure thereof is hereby incorporated by reference.
  • the preferred acid dyes useful in the invention are the monosulfated acid dyes and 2:1 metal complexed acid dyes (2 moles of acid dye to 1 mole of metal).
  • the vinyl sulfone dyes used in the following examples are illustrative of the vinyl sulfone dyes that may be used in this invention.
  • the structures of these dyes are shown in Table 1 in their free acid form wherein the dyes are designated Yellow 1, Yellow 2, Yellow 3, Red 1, Blue 1, Blue 2, Orange 1 and Black 1 for reference purposes.
  • the acid dyes used in the following examples are acid dyes and are referenced by their Color Index (CI) number.
  • Illustrative dyes useful in the invention are Acid Yellow 49, Acid Yellow 151 (2:1 premetallized), Acid Blue 277, Acid Orange 156, Acid Red 266, Acid Red 337, Acid Red 361, Acid Blue 277, Acid Blue 324, Acid Blue 158 (a pre metallized acid dye) Acid' Blue 78, Direct Red 185, and Acid Orange 156.
  • a 20 gram piece of nylon 6 carpet was dyed in an aqueous dye bath containing:
  • Remol ® is a registered trademark of Hoechst A.G., Frankfurt, Germany.
  • the bath was set at a pH of 3 at 80°F.
  • the bath was raised at a rate of 3°F/minute until it reached the boil.
  • trisodium phosphate was added to attain a pH of 12 and boiling continued for another 45 minutes.
  • the bath was dropped and the carpet was rinsed in cold water and dried. The dyeing was a rust color which was uniform in shade throughout.
  • test dyebath was prepared using:
  • SDDD sodium dodecyl diphenyloxide disulfonate
  • a 10 g swatch of dyed carpet was placed in the dyebath along with 10 g of greige carpet.
  • a dye cycle was run for 30 minutes at the boil, after which the pieces were removed, rinsed, and dried.
  • the bath was set at a pH of 3 at 80°F and then the same dyeing cycle as used in Example 1 was followed.
  • the resultant shade was greyish blue which was uniform in shade throughout.
  • Example 2 As in Example 1, a dye cycle was run in a test bath containing dyed and undyed carpet. There was no apparent change in the dyed piece of carpet and the greige piece was dyed a pale blue shade, equivalent to a 3 on the AATCC Grey Scale for evaluating staining.
  • a 20 gram piece of nylon 6 carpet was dyed in an aqueous dye bath containing:
  • the bath was set at a pH of 3 at 80°F and then the same dyeing cycle as used in Example 1 was followed.
  • the resultant shade is a deep lavender which is uniform in color.
  • the greige piece was slightly dyed a beige shade and the lavender piece was dulled and cast to the yellow side.
  • a dyeing was then made using the above Tectilon ® dye formula on 20 grams of greige carpet without the lavender piece being present.
  • the resultant beige shade was the same as the beige shade obtained when the lavender piece of vinyl sulfone dyed carpet was present. This showed that the vinyl sulfone dyes do not interfere with a subsequent overdyeing cycle and that the vinyl sulfone lavender sample was only slightly affected by the acid dyes.
  • Hostapur ® is a registered trademark of Hoechst A.G., Frankfurt, Germany.
  • the carpet was steamed 6 minutes and then removed and dipped in a 50 g/l solution of trisodium phosphate and steamed again for 6 minutes. The carpet was rinsed and dried.
  • Example 2 To check the amount of reactive bonding, 10 grams of the dyed carpet was placed in an exhaust dye bath with 10 grams of greige carpet. As in Example 1, a blank dye cycle was run for 45 minutes at the boil at a pH of 7.0 with no chemicals present. The result was that the greige carpet was dyed a pale orange shade, equivalent to a 2 on the Grey Scale for evaluating staining.
  • a dye having one vinyl sulfone and one SO 3 substituent had the least overdye fastness; followed by the dye having one vinyl sulfone and two SO 3 substituents (Yellow 1).
  • the best dye was the Yellow 2 dye having two vinyl sulfone and one SO 3 substituents.
  • the processing sequence was: pad dye
  • one of the pieces was thermofixed at a temperature of 325°F for 20 minutes, which simulates the curing cycle when the rubber backing is bonded to the carpet in the manufacture of the washable mats.
  • a laundry cycle was carried out on each of the two dyed pieces along with a greige blank.
  • the bath was held at 160oF for 2 hours and contained 1.0 g/l of a commercial detergent which gave the bath a pH of 9.4.
  • Example 7 and the same wash tests were performed. In the case of the sample which had been dried only, there was only a slight loss of color after the wash cycle. The sample which had been thermofixed showed no loss of color.
  • a piece of nylon 6-6 carpet was printed with dark red and dark maroon dots and then flooded with a heavy red shade using the following formula:
  • Example 7 The above sample of carpet was fixed following the procedure in Example 7, including the thermofixation cycle. Also as in Example 7, a wash cycle was carried out on the carpet and no loss of shade or deposition was observed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

Procédé de teinture de polyamides à l'aide de teintures réactives hydrosolubles comprenant le substituant réactif (SO2-Z) dans lequel 'Z' est un groupe réagissant avec les fibres. Au moins une teinture réagissant avec les fibres est appliquée au substrat de polyamide à un pH acide et le substrat teint est ensuite chauffé avec un composé alcalin et de la chaleur de manière à fixer de manière covalente la teinture au substrat. Le polyamide teint de manière covalente a une solidité et des propriétés de surteinture supérieures à celles des substrats de polyamide teints à l'aide de teintures acides.
PCT/US1992/001866 1991-03-11 1992-03-09 Procede de teinture de substrats en polyamide WO1992015750A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66772691A 1991-03-11 1991-03-11
US667,726 1991-03-11

Publications (1)

Publication Number Publication Date
WO1992015750A1 true WO1992015750A1 (fr) 1992-09-17

Family

ID=24679381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/001866 WO1992015750A1 (fr) 1991-03-11 1992-03-09 Procede de teinture de substrats en polyamide

Country Status (2)

Country Link
EP (1) EP0575541A1 (fr)
WO (1) WO1992015750A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0760838A1 (fr) * 1994-05-24 1997-03-12 Hoechst Celanese Corporation Compositions colorantes pour polyamides

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775045A (en) * 1970-06-11 1973-11-27 Ciba Geigy Ag Process for the production of multi-colour effects on natural and synthetic polyamide fibre material
US4218217A (en) * 1974-04-01 1980-08-19 Sandoz, Inc. Method of producing multicolor dyeings
US4680033A (en) * 1984-10-29 1987-07-14 Hoechst Aktiengesellschaft Process for producing white and colored resists on polyamide fiber materials using reactive dye in free vinyl sulphone form
US4878920A (en) * 1987-04-28 1989-11-07 Burlington Industries, Inc. Process for the continuous dyeing of industrial nylon
US4911735A (en) * 1985-12-18 1990-03-27 Hoechst Aktiengesellschaft Process for dyeing wool

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775045A (en) * 1970-06-11 1973-11-27 Ciba Geigy Ag Process for the production of multi-colour effects on natural and synthetic polyamide fibre material
US4218217A (en) * 1974-04-01 1980-08-19 Sandoz, Inc. Method of producing multicolor dyeings
US4680033A (en) * 1984-10-29 1987-07-14 Hoechst Aktiengesellschaft Process for producing white and colored resists on polyamide fiber materials using reactive dye in free vinyl sulphone form
US4911735A (en) * 1985-12-18 1990-03-27 Hoechst Aktiengesellschaft Process for dyeing wool
US4878920A (en) * 1987-04-28 1989-11-07 Burlington Industries, Inc. Process for the continuous dyeing of industrial nylon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0575541A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0760838A1 (fr) * 1994-05-24 1997-03-12 Hoechst Celanese Corporation Compositions colorantes pour polyamides
EP0760838A4 (fr) * 1994-05-24 1997-07-23 Hoechst Celanese Corp Compositions colorantes pour polyamides

Also Published As

Publication number Publication date
EP0575541A4 (fr) 1994-02-09
EP0575541A1 (fr) 1993-12-29

Similar Documents

Publication Publication Date Title
EP0490675B1 (fr) Procédé de teinture de substrats mixtes anioniques/cationiques polyamide
EP0490676B1 (fr) Procédé de préparation de substrats polyamide teints multicolorés
US5447539A (en) Method of dyeing polypropylene fiber with more than one color
US4455147A (en) Transfer printing
US3988108A (en) Process for coloring fibrous structures
US4411665A (en) Dyeing process using alkoxylated fatty amines and polyamines as reserving agents
US5512064A (en) Process for modifying and dyeing modified fiber materials
US5925149A (en) Method for dyeing nylon fabrics in multiple colors
CA1127355A (fr) Methode de teinture ou d'impression d'un substrat textile plan
EP0609268A4 (en) Process and composition for dyeing polymeric fibers.
EP0151370B1 (fr) Teinture et impression de fibres
US4063877A (en) Dyeing methods
WO1995030794A1 (fr) Procede de fixation de colorants dans des matieres textiles
JPH0152516B2 (fr)
US3314743A (en) Processes for treatment of preformed articles of olefin polymers and resulting products
US5484455A (en) Cationic dyeable nylon dyed with vinyl sulfone dyes to give overdye fastness
WO1992015750A1 (fr) Procede de teinture de substrats en polyamide
USRE36668E (en) Method of producing dyed nylon walk-off mats having improved washfastness, and mats produced thereby
Gutjahr et al. Direct print coloration
US3208814A (en) Process of coloring textile materials which comprises cross-linking the textile to awater-soluble dyestuff through a tris aziridinyl phosphine compound
AU609460B2 (en) Dyeing and printing fibres
GB2147319A (en) Level dyeing of wool fibres
GB2102454A (en) Process for producing multicoloured anionic dyeings
US3998586A (en) Process for the differential dyeing of polyamide fibers and of materials containing them
US3995993A (en) Process for the differential dyeing of polyamide fibers and of materials containing them

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 1992909109

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1992909109

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1992909109

Country of ref document: EP