EP0267681A2 - Traiter des articles en polyamides fibreux - Google Patents

Traiter des articles en polyamides fibreux Download PDF

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Publication number
EP0267681A2
EP0267681A2 EP87308464A EP87308464A EP0267681A2 EP 0267681 A2 EP0267681 A2 EP 0267681A2 EP 87308464 A EP87308464 A EP 87308464A EP 87308464 A EP87308464 A EP 87308464A EP 0267681 A2 EP0267681 A2 EP 0267681A2
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EP
European Patent Office
Prior art keywords
polyamide material
water
novolak resin
polyamide
soluble
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EP87308464A
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German (de)
English (en)
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EP0267681B1 (fr
EP0267681A3 (fr
Inventor
George L. C/O Minnesota Mining And Payet
John Cheng-Chung C/O Minnesota Mining And Chang
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3M Co
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Minnesota Mining and Manufacturing Co
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Classifications

    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/41—Phenol-aldehyde or phenol-ketone resins
    • D06M15/412—Phenol-aldehyde or phenol-ketone resins sulfonated

Definitions

  • the present invention relates to a process for providing stain resistance to polyamide articles, such as nylon and wool carpets, nylon, wool, and silk fabrics, and natural and synthetic leathers.
  • Fibrous polyamide articles such as nylon and wool carpets, nylon, wool, and silk fabric, natural leather, and synthetic leathers such as UltrasuedeTM are particularly susceptible to staining by natural and artificial acid colorants such as are commonly found in many foods and beverages.
  • a need has long been felt for processes for economically providing such fibrous polyamide articles with resistance to staining by acid colorants.
  • U.S. Patent No. 4,501,591 discloses a process for providing stain-resistant polyamide carpets in which a sulfonated phenol-formaldehyde condensation product and an alkali metal silicate are added to the dye liquor in a continuous dyeing process, followed by steaming, washing, and drying the carpet.
  • U.S. Patent No. 4,592,940 (Blyth et al.) discloses a process for imparting stain resistance to nylon carpet by immersing the carpet in a boiling aqueous solution of a selected phenol-formaldehyde condensation product at a pH of 4.5 or less. The process is carried out in conventional beck dyeing apparatus subsequent to dyeing (generally at a pH of 6.5 to 8.0) by either acidifying the bath to pH 4.5 or less or draining the dye bath and then replacing the dye bath with a corresponding amount of water adjusted to pH 4.5 or less. Blyth et al. disclose that insufficient condensation product for imparting stain resistance is picked up by the carpet at pH greater than 4.5 and temperature less than 95°C.
  • U.S. Patent No. 4,579,762 discloses stain-resistant nylon carpet in which the nylon fibers are made from polymer modified to contain, as an integral part of its polymer chain, sufficient aromatic sulfonate units to improve the acid dye resistance of the fibers and in which the backing adhesive contains a fluorochemical in an amount sufficient to render the backing a barrier to liquids.
  • Japanese Examined Patent Application Korean Unexad Patent Application (Kokoku) No. 48-8789 (1973) (Meisei) discloses a method for treatment of dyed polyamide fibers to improve anti-static and anti-melting properties and moisture resistance in which a ligand oligomer, formed from sulfonated 4,4 ⁇ -dihydroxy-diphenyl sulfone-formaldehyde condensate with a metal compound prepared from citric acid and a metal chloride, metal oxide, or organic metal salt, is applied to fiber from a treatment bath or, alternatively, the sulfonated 4,4 ⁇ -dihydroxy-diphenyl sulfone-formaldehyde condensate and a metal compound prepared from a metal salt, citric acid and hydroxy acetic acid, are added to the treatment bath separately.
  • a ligand oligomer formed from sulfonated 4,4 ⁇ -dihydroxy-diphenyl sulfone-formal
  • U.S. Patent No. 4,329,391 discloses the treatment of synthetic fibers with a sulfonated polyester stain-releasing finish in an aqueous bath which includes the addition of water-soluble salts to the aqueous fabric treating bath.
  • the treatment provides a finish which enhances oily soil release during after-stain laundering.
  • U.S. Defensive Publication T949,001 discloses a process for improving the durability of water-dispersible polyester and polyester amide textile finishes on fabric where the fabric, after application of the finish, is treated with an aqueous solution of polyvalent metal salts.
  • U.S. Patent No. 3,322,488 discloses sulfomethylated condensation products of bisphenols and aldehydes for use in reserving synthetic polyamide and polyurethane fibers to render them resistant to acid and direct dyes.
  • U.S. Patent No. 3,663,157 discloses a process for printing nylon fabric with disperse or monosulfonated acid dyes wherein the fabric is pretreated with an aqueous solution of a fiber-substantive, water-soluble, anionic resist which is a polycondensate of a diarylsulfone containing at least one phenolic hydroxy group with formaldehyde.
  • U.S. Patent No. 3,926,548 discloses aminated hydrophobic fibers having a surface resistant to anionic dyes, the surface of the fibers having been treated with a compound having groups capable of linking to amino groups in the fibers to form covalent bonds.
  • groups include halotriazinyl, halopyrimidinyl, haloquinoxalyl, haloacrylamido, vinylsulfo groups, etc., or any other groups that can produce these groups.
  • compounds having anionic groups for example, sulfonate, carboxylate, sulfate, phosphate groups, etc., besides the highly reactive groups capable of reacting with amino groups.
  • U.S. Patent No. 3,959,559 discloses a process for producing modified synthetic fibers in which the fibers are treated with a reaction product of a specified s-triazine or piperazine derivative, with a specified derivative of polyoxyethylene and further adhering onto the resulting fibers a specified aromatic sulfonic acid.
  • the modified fibers resist contamination from liberated dyestuff or ionic contaminants during laundering or dry cleaning.
  • U.S. Patent No. 4,322,512 discloses treating a polyamide textile material with a substituted trimellitic anhydride compound, the treatment decreasing the textile material's affinity for acid dyes.
  • U.S. Patent No. 4,343,923 discloses a method for decreasing a textile material's affinity for acid dyes in which the textile material is pretreated with an acylimidazole compound.
  • U.S. Patent No. 4,563,190 discloses a dyeing assistant useful in the dyeing of polyamide fibers with acid dyes.
  • the dyeing assistant is a mixture of (A) a sulfonated condensation product of hydroxyaryl compounds and formaldehyde or a sulfonated N-aryl-melamine derivative, and (B) a specified quaternary ammonium, and, optionally, (C) a siloxane/oxyalkylene copolymer and (D) a polar solvent.
  • European Patent Appln. No. 83,303,341.8 discloses increased exhaustion of fluorochemical treating agents for providing oil and water repellency by the addition of salt compounds such as sodium sulfate and citrate, magnesium chloride, ammonium sulfate and chloride, aluminum sulfate, calcium chloride, and potassium chloride.
  • U.S. Patent No. 4,013,627 discloses a fluorochemical polymer for treating fabrics to provide oil and water repellency, the polymer being derived from fluorochemical acrylate monomer, a vinyl monomer free of non-vinylic fluorine, and a vinyl monomer which contains an onium ionic group. Salts, such as alkali metal sulfates and low molecular weight alkylamine hydrochlorides, may be added, as adjuvants, to textile treating baths containing the fluorochemical polymer to aid deposition of the polymer onto the fabric being treated.
  • Salts such as alkali metal sulfates and low molecular weight alkylamine hydrochlorides
  • the present invention provides a method for providing fibrous polyamide material with stain resistance to natural and artificial acid colorants comprising contacting the fibrous polyamide material with an aqueous solution comprising a normally solid, water-soluble, partially sulfonated novolak resin, which comprises the condensation product of at least one phenolic compound and an aldehyde such as, for example, formaldehyde or acetaldehyde, and a water-soluble divalent metal salt.
  • the resin and salt are applied in sufficient amounts and for sufficient time at a given temperature to provide stain resistance.
  • the combination of the sulfonated novolak resin and divalent metal salt provides surprising effective stain resistance using reduced amounts of the resin and permits application over a wide pH range.
  • One method comprises the steps of
  • a second method comprises the steps of
  • a third method comprises the steps of
  • the invention further provides including a fluorochemical composition in the aqueous solution comprising the sulfonated novolak resin and the divalent salt in step Ia, IIa, or IIIa to provide the polyamide material with oil and water repellency.
  • the invention further provides an aqueous solution useful in providing stain resistance to fibrous polyamide material comprising the water-soluble partially sulfonated novolak resin and the water-soluble divalent salt.
  • the invention also provides fibrous polyamide materials such as nylon, silk, and wool fabrics, yarns, and fibers, nylon and wool carpets, and natural and synthetic leather such as UltrasuedeTM with stain resistance by treating the polyamide materials as described in method I, II, or III hereinabove.
  • the present invention still further provides fibrous polyamide materials with stain resistance and oil and water repellency by treating the polyamide material, as described in method I, II, or III hereinabove, with a fluorochemical composition added to the treating solution.
  • the sulfonated novolak resins useful in this invention include known substances such as those compositions which are condensation products of formaldehyde with bis(hydroxyphenyl)sulfone and phenylsulfonic acid.
  • formaldehyde instead of, or in addition to, formaldehyde, another aldehyde such as, for example, acetaldehyde, furfuraldehyde, or benzaldehyde, can be used to make the condensation product.
  • phenolic compounds such as, for example, bis(hydroxyphenyl)alkane, e.g., 2,2-bis(hydroxyphenyl)propane, and bis(hydroxyphenyl) ether compounds can be used instead of, or in addition to the bis(hydroxyphenyl)sulfone.
  • the sulfonated novolak resin is partially sulfonated, i.e., has a sulfonic acid equivalent weight of about 300-1200, preferably 400-900. Examples of such resins are disclosed in U.S. Patent No. 4,592,940 (Blyth et al.) which is incorporated herein by reference for this purpose.
  • sulfonated novolak products such as IntratexTM N, available from Crompton and Knowles Corp., and ErionalTM PA, available from Ciba-Geigy Corp., NylofixanTMP available from Sandoz Ltd. MesitolTM NBS, available from Mobay Chemical Corp., Resist #4, available from Lyndal Chemical Co., AmeriolateTM, available from American Emulsions Co. Inc. and SynthabondTM 1938 available from Piedmont Chemical Industries.
  • Sulfonation of phenolic compounds is taught, for example, in Sulfonated and Related Reactions , E. E. Gilbert, Interscience Publishers, (1965). Condensation of phenol-formaldehyde resins is taught, for example, in Phenolic Resins , A. Knop et al., Springer-Verlag, (1985).
  • the divalent metal salts useful in the present invention include water soluble inorganic and organic salts of metals such as magnesium, barium, calcium, and zinc.
  • Inorganic metal salts include chlorides, sulfates, and nitrates of these metals.
  • Organic metal salts include acetates and formates of these metals.
  • Preferred divalent metal salts are magnesium sulfate, magnesium chloride and magnesium acetate. Mixtures of two or more salts can also be used in this invention.
  • magnesium salts are preferably used to achieve both stain resistance and oil and water repellency.
  • the fluorochemical compositions useful in the present invention for providing oil and water repellency include anionic, cationic, or nonionic fluorochemicals such as the fluorochemical allophanates disclosed in U.S. Patent No. 4,606,737 (Stern); fluorochemical polyacrylates disclosed in U.S. Patent Nos. 3,574,791 (Sherman et al.) and 4,147,851 (Raynolds); fluorochemical urethanes disclosed in U.S. Patent No. 3,398,182 (Guenthner et al.); fluorochemical carbodiimides disclosed in U.S. Patent No. 4,024,178 (Landucci); fluorochemical guanidines disclosed in U.S. Patent No. 4,540,497 (Chang et al.).
  • anionic, cationic, or nonionic fluorochemicals such as the fluorochemical allophanates disclosed in U.S. Patent No. 4,606,737 (Stern); fluorochemical polyacryl
  • the sulfonated novolak resins are preferably used in an amount of at least 0.1% solids owf, more preferably 0.15% owf, most preferably at least 0.35% owf. Amounts in excess of 3% owf generally do not provide any appreciable increase in stain resistance.
  • the amount of sulfonated novolak resin required to provide adequate stain resistance depends on the fibrous polyamide material being treated. For example, nylon 6 and wool generally require larger amounts of the resin than nylon 66.
  • yarn heat-set under moist conditions e.g., in an autoclave, generally requires larger amounts of the resin than with yarn heat-set under substantially dry conditions.
  • the divalent metal salts are preferably used in an amount of at least 1% owf, more preferably at least 1.5% solids owf, most preferably at least 2% solids. Amounts of the salt in excess of 5% owf generally do not provide any appreciable increase in stain resistance.
  • the fluorochemical composition when included in the treating solution, is preferably present in an amount of at least about 0.15% solids owf, more preferably at least 0.2% solids owf, most preferably 0.35% owf. Generally, amounts of the fluorochemical composition in excess of 2% solids owf do not appreciably improve the oil and water repellency. Generally, when the polyamide material is nylon fiber, smaller denier fiber requires larger amounts of the fluorochemical composition than larger denier fiber.
  • the sulfonated novolak resin and water-soluble divalent metal salt can be applied from an aqueous exhaust bath such as is used in beck dyeing of carpet.
  • the sulfonated novolak resin and the water soluble divalent metal salt can be added to the aqueous dye bath solution and exhausted concurrently with the dye.
  • the dye bath is maintained at a temperature at or near the boiling point for a period of 10 to 90 minutes or more to effect exhaustion of the dye and the sulfonated novolak resin.
  • the dye bath can be maintained in the normal pH rang of 4.5 to 8.0 with excellent results.
  • Dye bath pH can range from 2.0 to 12.0, although pH in the range of 4 to 7 is preferred.
  • the sulfonated novolak resin and the water-soluble divalent metal salt can be added to the aqueous dye bath after exhaustion of the dye or the dyebath can be drained and fresh water added prior to the addition of the sulfonated novolak resin and the water-soluble divalent metal salt.
  • the resin/salt bath is maintained at a temperature at or near boiling for a period of time sufficient to exhaust the resin, usually 10 to 90 minutes.
  • the sulfonated novolak resin and divalent metal salt can be applied during continuous dyeing, such as with KusterTM or OttingTM carpet dyeing equipment.
  • the sulfonated novolak resin and the water-soluble divalent metal salt can be added directly to the aqueous dye solution and the solution is conventionally applied to the polyamide carpet.
  • the sulfonated novolak resin and the water-soluble metal salt can be applied during a wetting out step prior to application of the dye.
  • the carpet is then steamed, as usual, for 3 to 5 minutes.
  • the sulfonated novolak resin and divalent salt can also be applied to polyamide material by a padding operation. This can be done as a separate step or in conjunction with the application of various convention finishes such as wetting agents, softeners, and leveling agents. After application of the resin/salt solution, the polyamide material is conventionally dried.
  • Fluorochemical compositions for providing oil and water repellency can also be applied in conjunction with the sulfonated novolak resin.
  • the fluorochemical composition is simply added in an appropriate amount to the treating solution.
  • useful divalent metal salts may be limited to the inorganic and organic magnesium salts.
  • SPFR sulfonated phenol-formaldehyde resin
  • the resulting sulfonated 4,4 ⁇ -dihydroxy­diphenylsulfone-formaldehyde condensate was diluted with 1400 g of water and neutralized to a pH of 6.0 with 550 g of 5% NaOH to yield the sodium salt of the partially sulfonated novolak resin product as a 36% aqueous concentrate (SPFR).
  • fibrous polyamide materials were evaluated using the following test methods:
  • a 1 g sample of the fibrous polyamide material under evaluation is placed in 40 ml aqueous solution containing 0.008 weight percent FD&C Red Dye No. 40 and 0.04 weight percent citric acid at room temperature (22°C) and agitated for one hour.
  • the sample is removed from the dye solution, rinsed and blotted with paper towels to remove excess moisture.
  • the amount of staining is evaluated visually using a rating scale which ranges from 1-5, where 1 is essentially unstained and 5 is heavily stained. Generally, a stain resistance of less than 3 is satisfactory.
  • the water repellency of treated polyamide samples is measured using a water/isopropyl alcohol test, and is expressed in terms of a water repellency rating on a scale of 0 to 10 of the treated carpet or fabric.
  • Treated carpets which are penetrated by or resistant only to a 100 percent water/0 percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given a rating of 0, whereas treated fabrics resistant to a 0 percent water/100 percent isopropyl alcohol mixture (the most penetrating of the test mixtures) are given a rating of 10.
  • Other intermediate values are determined by use of other water/isopropyl alcohol mixtures, in which the percentage amounts of water and isopropyl alcohol are each multiples of 10.
  • the water repellency rating corresponds to the most penetrating mixture which does not penetrate or wet the fabric after 10 seconds contact. In general, a water repellency rating of at least 1, is desirable for carpet.
  • the oil repellency of the treated polyamide samples is measured by AATCC Standard Test 188-1978, which test is based on the resistance of treated fabric to penetration by oils of varying surface tensions. Treated fabrics resistant only to NujolTM, a brand of mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetrating of the test oils) are given a value of 8. Other intermediate values are determined by use of other pure oils or mixtures of oils. The rated oil repellency corresponds to the most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric after 10 seconds contact rather than the 30 seconds contact of the Standard Test. Higher numbers indicate better oil repellency. Additionally, a value of 0 indicates no resistance to NujolTM. In general, an oil repellency of at least 1 or greater is desirable for carpet.
  • the use of divalent magnesium salts provides significantly better stain resistance to the carpet than does the use of the monovalent salts, ammonium sulfate and sodium chloride, even when relatively large amounts (5% owf) of the monovalent salts are used.
  • Example 4-7 samples of nylon 66 carpet which had been heat-set for 10 minutes at 150°C under substantially dry conditions, were immersed for 90 minutes in an aqueous solution at 97°C and a pH of 6 and a liquor to fabric ratio of 20:1 using 0.2% owf SPFR with 2% solids owf of various salts.
  • Comparative Example C5 no SPFR or salt were used and, in Comparative Example C6, SPFR was used without salt.
  • Example 8 and Comparative Examples C7-C9 0.25% owf of a fluorochemical oil, and water repellent composition, FX-364, available from 3M Company, was added to the treating solution containing SPFR and salt. Each sample was removed from the solution, rinsed, and dried for 10 minutes at 70°C and then for 5 minutes at 130°C. Each sample was tested for stain resistance (SR), oil repellency (OR), and water repellency (WR). The results are shown in Table 2.
  • Samples of chamois (natural leather) and upholstery-weight, nylon UltrasuedeTM (synthetic leather) were treated by immersing the sample in water or in aqueous solutions containing 0.35% solids owf SPFR and 2% owf magnesium acetate at room temperature at a liquor to fabric ratio of 20:1 for 46 hours. Each sample was removed from the treating solution, rinsed and dried for 10 minutes at 70°C and then for 5 minutes at 130°C. Each sample was tested for stain resistance (SR), the results are set forth in Table 5.
  • SR stain resistance
  • Samples of nylon 66 level loop carpet which had been heat-set for 10 minutes at 150°C under substantially dry conditions were dyed by immersing the samples in aqueous solutions at various pH's using 0.35% solids owf SPFR with and without 2% owf magnesium acetate at a liquor to fabric ratio of 20:1, a treatment temperature of 97°C, a pH of about 6 and a treatment time of 90 minutes in a Launderometer.
  • a sample also was treated with water only. Each sample was removed from the treating solution, rinsed, and dried for 10 minutes at 70°C and then for 5 minutes at 130°C. Each sample was tested for stain resistance (SR). The results are shown in Table 6.
  • nylon upholstery fabric which had been heat-set for 10 minutes at 150° under substantially dry conditions, was treated by padding (50% wet pick up) an aqueous solution containing 0.3% solids owf SPFR with and without 2% owf magnesium chloride salt, and with and without a 0.3% solids owf of a blend of fluorochemical oil and water repellent composition, FC-214, available from 3M Company (FC).
  • FC-214 fluorochemical oil and water repellent composition
  • FC-214 fluorochemical oil and water repellent composition
  • samples of nylon 66 level loop carpet which had been heat-set under substantially dry conditions for 1 minute at 200°C were treated by immersion in an aqueous bath at a liquor to fabric ratio of 21.5:1, at treating temperature of 97°C, and a treatment time of 90 minutes with 0.3% solids owf SPFR various commercial novolak resins (NR) with and without 2% owf magnesium chloride and with and without 0.25% solids owf of a fluorochemical composition, FX-364, available from 3M Company (FC).
  • the pH was adjusted to 3.5 with acetic acid.
  • the samples were removed from the treating solution, rinsed, and dried for 10 minutes at 70°C and then for 5 minutes at 130°C.
  • the samples were tested for stain resistane (SR), oil repellency (OR), and water repellency (WR). The results are shown in Table 8.
  • the dye bath pH was 6.0.
  • the carpet was removed from the dye bath and steamed at 100°C, 100% r.h. for 5 minutes, dried for 20 minutes at 70°C. and set at 130°C for 10 minutes. The samples were tested for stain resistance. The results are shown in Table 10.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP87308464A 1986-10-14 1987-09-24 Traiter des articles en polyamides fibreux Revoked EP0267681B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US91837686A 1986-10-14 1986-10-14
US918376 1986-10-14

Publications (3)

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EP0267681A2 true EP0267681A2 (fr) 1988-05-18
EP0267681A3 EP0267681A3 (fr) 1991-03-13
EP0267681B1 EP0267681B1 (fr) 1993-03-10

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EP87308464A Revoked EP0267681B1 (fr) 1986-10-14 1987-09-24 Traiter des articles en polyamides fibreux

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EP (1) EP0267681B1 (fr)
AU (1) AU604504B2 (fr)
CA (1) CA1339878C (fr)
DE (1) DE3784631T2 (fr)
ZA (1) ZA877686B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
WO1991003593A1 (fr) * 1989-09-11 1991-03-21 Invicta Group Industries Pty Ltd Traitement de produits textiles utilisant de la triazine comme agent de liaison et un hydroxy aromatique sulfone comme agent de barriere
US5015259A (en) * 1989-04-20 1991-05-14 Peach State Labs, Inc. Stain resistant polymeric composition
US5061763A (en) * 1989-04-20 1991-10-29 Peach State Labs, Inc. Stain resistant treatment for polyamide fibers
WO1993021375A1 (fr) * 1992-04-14 1993-10-28 E.I. Du Pont De Nemours And Company Agents phenoliques resistant aux taches
WO1993022488A1 (fr) * 1992-04-30 1993-11-11 E.I. Du Pont De Nemours And Company Agents phenoliques de resistance aux taches
US5310828A (en) * 1989-04-20 1994-05-10 Peach State Labs, Inc. Superior stain resistant compositions
US5520962A (en) * 1995-02-13 1996-05-28 Shaw Industries, Inc. Method and composition for increasing repellency on carpet and carpet yarn
WO2006108240A1 (fr) * 2005-04-14 2006-10-19 Feltex Australia Pty Ltd Procédé de traitement de tapis
US7335234B2 (en) 2002-10-16 2008-02-26 Columbia Insurance Company Method of treating fibers, carpet yarns and carpets to enhance repellency

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1276410C (fr) * 1986-02-14 1990-11-20 Theodor A. Liss Textiles resistant a la souillure
US6524492B2 (en) 2000-12-28 2003-02-25 Peach State Labs, Inc. Composition and method for increasing water and oil repellency of textiles and carpet

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2934980A1 (de) * 1979-08-30 1981-03-19 Bayer Ag, 5090 Leverkusen Phenol-formaldehyd-kondensate, ihre herstellung und verwendung als dispergiermittel, verfluessiger und gerbstoffe
US4457874A (en) * 1981-08-19 1984-07-03 Diamond Shamrock Chemicals Company Condensation products of substituted phenol sulfonic acid and formaldehyde
US4592940A (en) * 1983-12-16 1986-06-03 Monsanto Company Stain-resistant nylon carpets impregnated with condensation product of formaldehyde with mixture of diphenolsulfone and phenolsulfonic acid
CA1264505A (fr) * 1986-02-14 1990-01-23 E.I. Du Pont De Nemours And Company Procede de fabrication de polyamides resistant aux taches
CA1276410C (fr) * 1986-02-14 1990-11-20 Theodor A. Liss Textiles resistant a la souillure
AU599427B2 (en) * 1986-11-14 1990-07-19 Minnesota Mining And Manufacturing Company Divalent metal salts of sulfonated novolak resins and methods for treating fibrous polyamide materials therewith

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
US5015259A (en) * 1989-04-20 1991-05-14 Peach State Labs, Inc. Stain resistant polymeric composition
US5061763A (en) * 1989-04-20 1991-10-29 Peach State Labs, Inc. Stain resistant treatment for polyamide fibers
US5310828A (en) * 1989-04-20 1994-05-10 Peach State Labs, Inc. Superior stain resistant compositions
WO1991003593A1 (fr) * 1989-09-11 1991-03-21 Invicta Group Industries Pty Ltd Traitement de produits textiles utilisant de la triazine comme agent de liaison et un hydroxy aromatique sulfone comme agent de barriere
WO1993021375A1 (fr) * 1992-04-14 1993-10-28 E.I. Du Pont De Nemours And Company Agents phenoliques resistant aux taches
AU663589B2 (en) * 1992-04-14 1995-10-12 E.I. Du Pont De Nemours And Company Phenolic stain-resists
WO1993022488A1 (fr) * 1992-04-30 1993-11-11 E.I. Du Pont De Nemours And Company Agents phenoliques de resistance aux taches
US5520962A (en) * 1995-02-13 1996-05-28 Shaw Industries, Inc. Method and composition for increasing repellency on carpet and carpet yarn
US7335234B2 (en) 2002-10-16 2008-02-26 Columbia Insurance Company Method of treating fibers, carpet yarns and carpets to enhance repellency
WO2006108240A1 (fr) * 2005-04-14 2006-10-19 Feltex Australia Pty Ltd Procédé de traitement de tapis

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DE3784631T2 (de) 1993-09-23
EP0267681B1 (fr) 1993-03-10
DE3784631D1 (de) 1993-04-15
EP0267681A3 (fr) 1991-03-13
ZA877686B (en) 1989-06-28
CA1339878C (fr) 1998-05-26
AU7865987A (en) 1988-04-21
AU604504B2 (en) 1990-12-20

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