EP0382724B1 - Verfahren zum erhöhen der fleckenbeständigkeit von teppichfasern - Google Patents

Verfahren zum erhöhen der fleckenbeständigkeit von teppichfasern Download PDF

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Publication number
EP0382724B1
EP0382724B1 EP88904055A EP88904055A EP0382724B1 EP 0382724 B1 EP0382724 B1 EP 0382724B1 EP 88904055 A EP88904055 A EP 88904055A EP 88904055 A EP88904055 A EP 88904055A EP 0382724 B1 EP0382724 B1 EP 0382724B1
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EP
European Patent Office
Prior art keywords
fiber
thiocyanate
condensate
sulfonated aromatic
weight
Prior art date
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EP88904055A
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English (en)
French (fr)
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EP0382724A1 (de
Inventor
Dale Alan Hangey
Paul Wesley Harris
Daniel Joseph Corcoran, Jr.
Michael Philip Friedberger
Charles Jayroe Cole
William Alexander Archie
Roger Neil Spitz
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Honeywell International Inc
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AlliedSignal Inc
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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
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides

Definitions

  • This invention is related to an improved method for exhausting a water-soluble thiocyanate onto polyamide fiber.
  • sulfonated aromatic condensate s.a.c.
  • any condensate of an aromatic compound whether sulfonated prior to or after condensation particularly sulfonated aromatic formaldehyde condensate (s.a.f.c.), effective to enhance stain resistance of fiber or carpet fabric.
  • thiocyanate any salt, organic or inorganic, containing a cation and the thiocyanate anion.
  • fluorocarbon is meant those fluorocarbon compounds effective to improve the antisoiling properties of fiber or carpet fabric.
  • ICP index of crystalline perfection, a measured indication of the internal crystal structure of the polymer in an oriented fiber.
  • High ICP indicates an open crystalline internal structure, easily dyeable polymer fiber.
  • nylon is meant the polyamide family of polymers, nylon 6, nylon 6,6, nylon 4, nylon 12 and the other polymers containing the structure along with the ⁇ CH2 ⁇ x chain.
  • carpet fabric carpet fiber or yarn which has been typically tufted, woven, or otherwise constructed into fabric suitable for final use in home furnishings, particularly as floor covering.
  • fiber is meant continuous filament of a running or extremely long length or cut or otherwise short fiber known as staple.
  • Carpet yarn may be made of multiple continuous filaments or spun staple fiber, both typically pretextured for increased bulk.
  • salt having a divalent cation is meant any such salt effective to enhance stain resistance of fiber, particularly high ICP nylon fiber, when combined with an effective amount of a s.a.c.
  • dispersing agent any chemical compound or combination of chemical compounds effective to make stable, relatively nonprecipitating, noncoagulating mixtures of other chemical compounds.
  • sequestering agent any chelating agent which is effective in sequestration, which is the suppression of certain properties of a metal without removing it from the system or phase. To be practical, the sequestering agent must not cause any undesirable change that would render the system unsuitable for its intended purpose. Chelation produces sequestration mainly by reducing the concentration of free metal ion to a very low value by converting most of the metal to a soluble chelate that does not possess the properties to be suppressed.
  • a chelating agent is a compound containing donor atoms that can combine by coordinate bonding with a single metal atom to form a cyclic structure called a chelation complex or, simply, a chelate. Because the donor atoms are connected intramolecularly by chains of other atoms, a chelate ring is formed for each donor atom after the first which coordinates with the metal. The above is from Volume 5, beginning page 339, of the Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley & Sons), 1979, hereby incorporated by reference to p. 367.
  • Nylon carpets may be permanently discolored or stained by certain artificial colorants, such as food dyes, or oxidizing agents, such as acne preparations containing benzoyl peroxide.
  • S.A.C.'s applied to the fiber to provide an ionic barrier to food colorants, make the fiber more stain resistant, but are not effective against oxidizing agents.
  • many of the s.a.c.'s used commercially for the preparation of "stain resistant" carpets are themselves, susceptible to oxidation upon exposure to light and ozone. This results in a yellowing of the s.a.c. and subsequent destruction. This has a major impact on the carpet properties.
  • the yellow color of the s.a.c. results in a perceptible shift in the color of the carpet. Destruction of the s.a.c. results in a loss of the stain resistance properties of the carpet.
  • fluorocarbon compound treated nylon fiber in carpet fabric inhibits wetting of the fiber surfaces which also inhibits any staining agent from being adsorbed onto or absorbed into the fiber. This surface wetting inhibition can be insufficient when the staining agent is dropped on the carpet with enough force to break the surface energy of the fluorocarbon surface barrier or not cleaned from the carpet and left in contact with fibers for extended time. Carpet treated with compositions containing s.a.c.'s must not interfere with the antisoiling properties of the fluorocarbon.
  • s.a.c. to the carpet fabric must be effective, economical, and compatible to both untreated and fluorocarbon treated fiber, and to both continuous dyeing and Beck or batch dyeing. The same is true of any s.a.c. application formulation.
  • the s.a.c. formulation must achieve effective penetration into the carpet fabric. Exhaustion of the individual active chemical components of any s.a.c. formulation must also be effective if not complete.
  • Certain nylon polymer fibers have very open internal crystal structure, namely high ICP polymer fiber, which require large amounts of s.a.c. to impart an effective degree of stain resistance.
  • High ICP polymers are usually the result of high temperature saturated steam heat setting processes.
  • compositions and methods are only marginally acceptable regarding durability of the stain resistance when the carpet is steam cleaned with a detergent at a high pH.
  • US-A-3387913, US-A-3576588 and US-A-3652199 refer to the application of thiocyanates at high pH as a dyeing aid.
  • US-A-3387913 discloses a method for producing dyeings and prints on cellulosic, polyester or polyamide fibers by applying water, a thiosulfuric acid derivative of sulfur dye, and a fixing agent.
  • Ammonium thiocyanate is one of a number of fixing agents disclosed in that document, for reducing fading of the dye.
  • US-A-3576588 discloses the use of a combination of ammonium thiocyanate and ammonium citrate to improve dye fixation by complexing with a basic dye in a printing paste.
  • US-A-3652199 discloses a process for improving dye diffusion when dyeing polyamide fibers with a cationic dye.
  • the fibers are treated at elevated temperature with an aqueous bath containing a cationic dye, and zinc thiocyanate.
  • the present invention provides a method for exhausting a water soluble thiocyanate onto polyamide fiber when said fiber is contacted with said thiocyanate, in which the contacting is carried out at a pH between 1 and 5, preferably between 1 and 4.
  • a pH between 1 and 5, preferably between 1 and 4.
  • the thiocyanate can be contacted with said fiber in a dyebath, or with said fiber after dyeing of said fiber.
  • the fiber can comprise a fluorocarbon to improve soiling of said fiber, and a sulfonated aromatic condensate can be present either on the fiber, or co-applied with the thiocyanate.
  • the amount of sulfonated aromatic condensate used can preferably comprise between 0.25 and 40 grams of solids of said condensate per liter of aqueous solution.
  • the sulfonated aromatic condensate is preferably formed by condensation of formaldehyde with one or more dihydroxy aromatic diphenol sulfones.
  • the condensate can be formaldehyde-condensed with an alkali metal salt of paraphenol sulfonic acid and with 4,4'-diphenolsulfone.
  • Thiocyanates can be used in a number of techniques for improving fiber properties.
  • the thiocyanates can be used with s.a.c., and with various added chemicals, to improve resistance of dye and s.a.c. on the fiber to oxidation.
  • Stain resistance of nylon fiber, particularly high ICP fiber can be improved using s.a.c., thiocyanate and a salt having a divalent cation and with additional added chemicals.
  • the carpet fabric can subsequently be washed in water.
  • the preferred sulfonated aromatic condensate has been condensed with formaldehyde.
  • the method of extracting can be by applying vacuum to the wet carpet fabric or by squeezing the wet carpet fabric with a pair of rollers.
  • the preferred concentration of the condensate is between 0.25 and 10 grams per liter of aqueous solution.
  • the preferred wet pick-up of the aqueous solution is between 300 and 600% by weight. When the aqueous solution is applied by pressurized contact with the carpet fabric, the wet pick-up preferred maximum is 450%. When the aqueous solution is applied by spray, the preferred wet pick-up mimimum is 400%.
  • the carpet fabric be held in the aqueous solution for between 2 and 30 seconds.
  • the preferred wet pick-up after extracting is between 50 and 150% by weight.
  • the sulfonated aromatic formaldehyde condensate can be formed by condensation of formaldehyde with one or more phenols. At least one of the phenols can be phenol sulfonic acid or the alkali metal salt thereof. It is preferred that one of the phenols be dihydroxy aromatic diphenylsulfone. It is most preferred that the condensate be formaldehyde condensed with the alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenylsulfone.
  • the beginning dyed carpet fabric of this process may also comprise an effective amount of a fluorocarbon compound intended to improve resistance to soiling of the carpet.
  • the preferred amount of fluorocarbon present is an amount of from 0.05 to 0.4% by weight of the fabric.
  • the fluorocarbon can contain perfluoroalkyl radical or can be a mixture of fluorinated pyromellitate oligomers.
  • a more preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first, the reaction of pyromellitic dianhydride with the fluorinated alcohol, and second, the reaction product of the first reaction further reacted with epichlorohydrin.
  • Another preferred fluorocarbon is a reaction product of a perfluoroalkyl alcohol or amide with a suitable anhydride or isocyanate.
  • Another more preferred fluorocarbon is a reaction product of N-ethyl perfluorooctyl-sulfoamideo ethanol with toluene diisocyanate.
  • the aqueous solution of this method will also contain an effective amount of a thiocyanate.
  • the thiocyanate cation may be ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl, preferred is ammonium.
  • the aqueous solution of this method may also contain an effective amount of a dispersing agent.
  • the dispersing agent can be a condensed naphthalenic salt, alkyl sulfosuccinate or mixtures thereof.
  • the preferred dispersing agent is a mixture of a sodium salt of condensed naphthalenic sulfonic acid and di-isobutyl sulfosuccinate.
  • the aqueous solution of this method may also contain an effective amount of a salt having a divalent cation.
  • the preferred salt is calcium, magnesium, zinc, or ferrous chloride, sulfate or phosphate wherein the most preferred is magnesium sulfate.
  • the preferred aqueous solution would contain the combination of a sulfonated aromatic condensate, a salt containing a divalent cation, the thiocyanate, and a dispersing agent, the most preferred combination would be wherein the condensate is formaldehyde condensed with the alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone, the thiocyanate is ammonium thiocyanate, the divalent cationic salt is magnesium sulfate and the preferred dispersing agents are di-isobutyl sulfosuccinate and the sodium salt of condensed naphthalene sulfonic acid in a mixture.
  • the preferred carpet fabric would comprise a fiber treated with a fluorocarbon.
  • the fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first the reaction of pyromellitic dianhydride with a fluorinated alcohol, second, the reaction product of the first reaction further reacted with epichlorohydrin.
  • the amounts of the fluorocarbon present on the carpet fabric used in the method is an amount between 0.05 and 0.4% by weight of the fabric
  • the magnesium sulfate can be present in the aqueous solution of the method in an amount between 0.05 and 0.8% on the weight of the fabric
  • the ammonium thiocyanate can be present in an amount in 0.03 to 1% on the weight of the fabric
  • the sulfonated aromatic condensate can be present in an amount of between 0.15 and 7.5% on the weight of the fabric
  • the dialkyl sulfosuccinate can be present in an amount of between 0 and 6 parts by weight to the parts by weight of the sulfonated aromatic condensate
  • the sodium of the condensed naphthalenic acid can be present in an amount between 0 and 3 parts by weight to parts by weight of the sulfonated aromatic condensate.
  • the preferred amounts of the compounds are 0.05 and 0.4% by weight of the fabric of the fluorocarbon, between 0.08 and 0.4% on the weight of the fabric of the magnesium sulfate, between 0.15 and 0.7% on the weight of the fabric of the ammonium thiocyanate and between 0.15 and 1.5% on the weight of the fabric of the sulfonated aromatic condensate with the dialkyl sulfosuccinate being present in an amount between 0 and 2.5 parts by weight to the parts by weight of the sulfonated aromatic condensate and the sodium salt of the condensed naphthalenic acid being present in an amount between 0 and 2 parts by weight to parts by weight of the sulfonated aromatic condensate.
  • any of the above aqueous solutions can be buffered with an effective amount of citric acid or any other acid with a sequestering agent.
  • the preferred aqueous solution is buffered with an amount of citric acid between 0.3 and 5.5 grams per liter of aqueous solution.
  • a two-step process embodiment of this invention uses the aftertreatment process described above but, preceding the initial preheating step of that aftertreatment an effective amount of the sulfonated aromatic condensate is added during dyeing of the carpet fabric so that the total of effective amounts of sulfonated aromatic condensate in both steps is less than the total effective amount useful in either the first dye step, solely, or in the subsequent application step, solely, or so that a more effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulfonated aromatic condensate in the two steps as compared to the same amount in either step solely.
  • An effective amount of the salt having a divalent cation can be added during the dyeing so that the s.a.c.
  • the divalent salt again can be calcium, zinc, magnesium or ferrous sulfate, chloride or phosphate.
  • the preferred salt is magnesium sulfate.
  • the preferred amounts of sulfonated aromatic condensate added during dyeing and after dyeing are from 0.05% on the weight of the fiber to 0.5% on the weight of the fiber during dyeing, an additional 0.05% on the weight of the fiber to 7.5% on the weight of the fiber after dyeing.
  • the preferred amounts of magnesium sulfate are 0.03 to 1% on the weight of the fiber added to the dyebath and 0.05 to 1% on the weight of the fiber added after dyeing.
  • the carpet fabric used in the method can comprise a fluorocarbon present before dyeing.
  • the fluorocarbon again can contain perfluoroalkyl radical or a mixture of fluorinated pyromellitic oligomers.
  • the preferred fluorocarbon is a mixture of pyromellitic oligomers formed by two reactions, first, the reaction of pyromellitic dianhydride with a fluorinated alcohol, and second, the reaction product of the first reaction further reacted with epichlorohydrin.
  • the preceding dyeing step can either be a continuous dyeing operation or it can be batch or beck dyeing.
  • the beck dyeing can be done in the presence of an effective amount of a salt having a divalent cation so that the stain resistance of the carpet fabric is enhanced.
  • the preferred amount of magnesium sulfate in the dyebath is an amount between 0.2% on the weight of the fiber to 5% on the weight of the fiber.
  • Another method to improve stain resistance of nylon or wool fiber comprises treating the fiber with a combination of an effective amount of each of a sulfonated aromatic condensate and a thiocyanate, whereby improved resistance to oxidation to ozone or by other strong oxidizing agents such as benzoyl peroxide is imparted to the s.a.c. and the dye on the fiber.
  • the preferred fiber is carpet fiber
  • the preferred aromatic condensate is sulfonated aromatic formaldehyde condensate formed by condensation with one or more phenols.
  • At least one of the phenols can be a phenol sulfonic acid or the alkali metal salt thereof. Or at least one of the phenols can be a sulfone.
  • the sulfone can be a dihydroxy aromatic diphenolsulfone.
  • the preferred condensate is formaldehyde condensed with a alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone.
  • This method of improving stain resistance of nylon or wool fiber using a thiocyanate with the sulfonated aromatic condensate can use a thiocyanate selected from the group consisting of ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl and phenyl thiocyanate. The most preferred is ammonium thiocyanate.
  • the dispersing agent can be added to the mixture applied to the fiber in this method also.
  • the dispersing agent can be selected from the group consisting of condensed naphthalenic salt, an alkyl sulfosuccinate or a mixture thereof.
  • the preferred dispersing agent is a mixture of the sodium salt of condensed naphthalene sulfonic acid and di-isobutyl sulfosuccinate.
  • the preferred amounts used in this method are between 0.05 and 10% on weight of the fiber of the sulfonated aromatic condensate, between 0.1 and 5% on weight of the fiber of the thiocyanate and the sodium salt of the condensed naphthalenic sulfonic acid is added in an amount between 0 and 3 parts by weight by parts by weight of the sulfonated aromatic condensate and the di-isobutyl sulfosuccinate is added in amount between 0 and 6 parts by weight to the parts by weight of sulfonated aromatic condensate.
  • Yet another method of improving stain resistance of nylon fiber, particularly fiber having a high index of crystalline perfection, for carpet comprises treating the fiber with a combination of an effective amount each of a sulfonated aromatic condensate, thiocyanate and salt having a divalent cation.
  • the sulfonated aromatic condensate can be a condensate with formaldehyde, can further be formed by the condensation of formaldehyde with one or more phenols and at least one of the phenols can be phenol sulfonic acid and the alkali metal salt thereof or sulfone.
  • the preferred condensate is formaldehyde condensed with a alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone.
  • the preferred thiocyanate is ammonium thiocyanate but the thiocyanate can be ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl.
  • the preferred salt is magnesium sulfate but the salt can be calcium, magnesium or ferrous chloride, sulfate or phosphate.
  • the fiber treated can comprise an effective amount of the fluorocarbon compound intended to enhance soil resistance of the fiber.
  • the preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first the reaction of pyromellitic dianhydride with a fluorinated alcohol and second a reaction product of the first reaction further reacted with epichlorohydrin.
  • a dispersing agent can be added to the combination used to treat the fiber in this method. Dispersing agents can be condensed naphthalenic salt or an alkyl sulfosuccinate or a mixture thereof.
  • the preferred amounts are between 0.15 and 7.5% on weight of the fiber of the sulfonated aromatic condensate between 0.15 and 1% on weight of the fabric of the thiocyanate, between 0.05 and 0.8% on weight of the fabric of the divalent cation salt, and between 0.05 and 0.4% on the weight of the fabric of the fluorocarbon present on the fiber before dyeing.
  • the condensate and thiocyanate can be buffered with an effective amount of citric acid or any acid with a sequestering agent so light induced yellowing of the stain resistant fiber is reduced.
  • Another two-step treatment is a method to dye and treat in two steps (both batch or beck) nylon carpet fabric to impart improved resistance to staining comprising dyeing in a first step in dyed carpet fabric in a dyebath liquor in the presence of an effective amount of a sulfonated aromatic condensate in an aqueous solution at an elevated temperature then removing the dyebath liquor from the dyed carpet fabric then rinsing the dyed carpet fabric then applying in a second step another effective amount of a sulfonated aromatic condensate in an aqueous solution to the dyed carpet fabric at a pH between 1.5 to 5.5 at a liquor temperature between 60 and 91°C (110 and 195°F) so that the total of effective amounts of sulfonated aromatic condensate in both steps is less than total effective amount useful in either the first dye steps solely or in a subsequent application step solely or so that a more effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulf
  • the dyeing conditions in the first step are a liquor to fabric ratio of 10:1 to 100:1 at a temperature of 70 to 100°C (158 to 212°F) for 15 to 90 minutes.
  • Preferred conditions for the second step are a liquor to fabric ratio of 10:1 to 100:1 for a period of 5 to 60 minutes.
  • the carpet fabric can be also rinsed subsequent to the second step.
  • the sulfonated aromatic condensate can be condensed with formaldehyde.
  • the sulfonated aromatic formaldehyde condensate can be formed by condensation of formaldehyde with one or more phenols.
  • the phenols can be phenol sulfonic acid or the alkali metal salt thereof.
  • the phenol can be dihydroxy aromatic diphenol sulfone.
  • the preferred condensate is formaldehyde condensed with alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone.
  • the dyed carpet fabric can comprise an effective amount of a fluorocarbon intended to improve the resistance of soiling of the carpet.
  • the preferred amount of the fluorocarbon is from 0.05 to 0.4% by weight on weight of the fabric.
  • the fluorocarbon can contain perfluoroalkyl radical or a mixture of fluorinated pyromellitate oligomers.
  • the fluorocarbon can be the reaction product of a perfluoroalkyl alcohol or amide with a suitable anhydride or isocyanate.
  • the fluorocarbon can be the reaction product of N-ethyl perfluorooctylsulfoamideo ethanol with toluene diisocyanate.
  • the preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first, the reaction of pyromellitic dianhydride with a fluorinated alcohol, and second, the first reaction product is further reacted with epichlorodrin.
  • the second step aqueous solution also contains an effective amount of a thiocyanate such as ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl thiocyanate.
  • the preferred thiocyanate is ammonium thiocyanate.
  • the aqueous solution of either or both application steps can also contain an effective amount of dispersing agent such a condensed naphthalenic salt, an alkyl sulfosuccinate or a mixture thereof.
  • the preferred dispersing agent is a mixture of the sodium salt of condensed naphthalene sulfonic acid and di-isobutyl sulfosuccinate.
  • the aqueous solutions of both steps of this invention can also contain an effective amount of salt having divalent cation such calcium, magnesium or ferrous chloride, sulfate or phosphate, preferably magnesium sulfate.
  • the preferred amounts of this method would be having the fluorocarbon present in an amount of 0.05 and 0.4% by weight of the fabric, magnesium sulfate present in an amount of between 0.25 and 4% on the weight of the fabric, ammonium thiocyanate present in an amount between 0.03 and 1% on the weight of the fabric, the sulfonated aromatic formaldehyde condensate present in an amount between 0.15 and 7.5% on the weight of the fabric and the dialkyl sulfosuccinate present in an amount betwen 0 and 6 parts by parts by weight of the sulfonated aromatic condensate and the sodium salt of a condensed naphthalenic acid is present in an amount between 0 and 3 parts by weight by parts by weight of sulfonated aromatic condensate.
  • the more preferred amounts are where the fluorocarbon is present in an amount of between 0.05 and 0.4% on the weight of the fabric, the magnesium sulfate is present in an amount between 0.25 and 1.5% on the weight of the fabric, ammonium thiocyanate is present in an amount between 0.05 and 0.75% on the weight of the fabric, sulfonated aromatic formaldehyde condensate is present in an amount between 0.15 and 2.0% on the weight of the fabric and the dialkyl sulfonsuccinate is present in an amount between 0 and 2.5 parts by weight to the parts by weight of the sulfonated aromatic condensate and the sodium salt of a condensed naphthalenic acid is present in an amount between 0 and 2 parts by weight to the parts by weight of the sulfonated aromatic condensate.
  • aqueous solution can be buffered with an effective amount of citric acid or any other acid with a sequestering agent to improve the yellowing of the carpet fabric.
  • Exhaustion of the water soluble thiocyanate onto polyamide fiber is achieved according to the invention by contacting the fiber with an effective amount of the thiocyanate at a pH between 1 and 5 whereby the fiber has improved resistance to fading of dye, due to strong oxidizing agents such as benzoyl peroxide or ozone, the dye being present in or on the fiber.
  • the thiocyanate can be ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl thiocyanate.
  • the preferred pH of the method is between 1 and 4.
  • the preferred amount of thiocyanate is between 0.1 and 6% on the weight of the fiber of the thiocyanate, present in or on the fiber after dyeing.
  • the method improves exhaustion so that between 0.1 and about 12% on the weight of the fiber of the thiocyanate is present during the contacting and at least 50% of the thiocyanate present during the contacting is exhausted onto or into the fiber.
  • the preferred thiocyanate is ammonium thiocyanate.
  • the thiocyanate can be contacted with the fiber in the dyebath or after dyeing of the fiber.
  • the fiber being treated can comprise an effective amount of a fluorocarbon to inhibit soiling of the fiber and a sulfonated aromatic condensate can be present either on the fiber or with the thiocyanate.
  • the various fluorocarbons are as described above.
  • An effective amount of citric acid or any acid with a sequestering agent can also be used to buffer for the condensate and thiocyanate to the desired pH for this same anti-yellowing effect. It is preferred to have between 0.1 and 12% thiocyanate on the weight of the fiber and between 0.05 and 0.4% fluorocarbon on the weight of the fiber.
  • This process is intended to continuously treat nylon carpet fabric with sulfonated aromatic condensate formulations, for instance on a continuous dye range after steaming but before washing; or piece (or beck) dyed carpets may be continuously treated in a similar fashion by treating in-line on the wet goods dryer range prior to the dryer.
  • Equipment could be a spray header(s), or the equivalent, for the heated water across the moving carpet fabric with vacuum extractors below or a set of squeeze rolls to remove the water, followed by spray headers for the treatment liquor with a catch pan underneath.
  • An alternative to spray application is use of a pressurized applicator, such as a Kusters Fluidyer, which presses the carpet into contact with a narrow slot in a conduit containing treatment liquor under pressure.
  • the prior art describes the application of similar sulfonated aromatic formaldehyde condensates by a beck (piece) aftertreatment and a continuous manner along with dyestuffs and subsequent steaming.
  • the continuous process of this invention has economical advantages over the beck aftertreatment process by approximately 4 cents per pound of fiber produced as finished carpet (at equal levels of the stain resist agent on the fiber).
  • the continuous aftertreatment process of this invention has the following advantages over the known prior art processes:
  • the process involves the general principle of first, preheating the carpet with heated water followed by hydroextraction and the application of an aqueous solution of the sulfonated aromatic formaldehyde condensate, for which there are specific ranges of pH, concentration, wet pick-up (w.p.u.) and temperatures. This is followed by a dwell period at which the carpet is either held at temperature or is allowed to radiant cool prior to washing the carpet.
  • the carpet Prior to the treatment, the carpet has already been dyed by either beck or continuous methods. For beck-dyed carpets the treatment process is at the wet goods dryer and for continuously-dyed carpets the treatment process is in-line after steaming and prior to the final washing step.
  • the process involves preheating the dyed carpet with hot water followed by hydroextraction by either squeeze or vacuum methods to a wet pick-up of 30 to 190%.
  • the conditions of the preheating process are established to achieve a carpet temperature of 130 to 210°F (54.4 to 99°C) prior to the treatment stage.
  • the conditions of the preheating process are generally using 200% w.p.u. to total saturation with water at 140 to 212°F (60 to 100°C).
  • this also gives the carpet a washing prior to application of the treatment solution which aids the carpet's receptiveness to the stain resist agent.
  • the treatment solution is an aqueous solution of the sulfonated aromatic condensate at a 0.25 to 40 grams per liter concentration and a pH of 1.5 to 5.5.
  • the treatment solution is applied at 200 to 600% w.p.u. add-on and a temperature of 140 to 212°F (60 to 100°C).
  • the resulting temperature of the carpet must be in the 130 to 210°F (54.4 to 99°C) range for the treatment to be effective. It is preferred to keep the difference in carpet fabric temperature between pretreating and application to a minimum. Following the application of the treatment liquor, it is necessary to either maintain the carpet at the application temperature for at least 0.5 to 30 seconds or allow it to radiantly cool to no less than 130°F (54.4°C).
  • the equipment used for the application of the treatment liquor may be either spray or contact (e.g. Kusters Fluidyer) in nature.
  • the contact method is preferred since it is easier to achieve 100% penetration of the treatment.
  • Spray processes are adequate provided that the solution penetrates to the back of the carpet, and will generally require additional mechanical considerations, such as squeeze or "S" rollers to achieve complete penetration.
  • Other application equipment may also be used as long as the process requirements of preheating, heated treatment and dwell time at temperature are satisfied.
  • the preheating and/or extracting steps may be carried out on the previously existing equipment.
  • the continuous aftertreatment technique can also be the second step of another two -step process embodiment of this invention wherein an effective amount of the sulfonated aromatic condensate is added to a continuous dyebath or in batch or beck process for dyeing carpet fabric.
  • the two-step process uses less overall amount sulfonated aromatic condensate for the same effect level of stain resistance.
  • the same total amount of sulfonated aromatic condensate can be used in the two-step process to achieve a higher level of stain resistance.
  • Certain nylon substrates have very open internal structure (orientation of the polymer chains) which require very high amounts of the sulfonated aromatic condensate composition to impart a marketable degree of stain resistance.
  • Certain sulfonated aromatic condensate compositions cannot achieve a sufficient level of protection on these substrates, so they must be excluded.
  • the continuous aftertreatment method results in only moderate durability of the stain resistance properties to steam cleaning when a high pH detergent is used.
  • the two-step application process has all of the advantages of the continuous aftertreatment process such as economics, etc. over one-step batch processes. It also has unique advantages over the aftertreatment process alone and all other known continuous application processes for sulfonated aromatic condensates, such as using all of the sulfonated aromatic condensate in dyebath (currently being practiced on a commercial scale).
  • the level of stain resistance imparted by a given total amount of the sulfonated aromatic condensate is substantially improved.
  • the required add-on for a marketable level of stain resistance reduced by approximately 30% over aftertreatment and greater for other continuous processes, providing economical advantages.
  • the process (with optimized sulfonated aromatic condensate composition for aftertreatment) yields marketable levels of stain resistance on critical substrates described above using reasonable levels of the sulfonated aromatic condensate composition.
  • the durability of the stain resistance properties to steam cleaning (with and without a high pH detergent) is improved over the aftertreatment only process, yielding improved properties.
  • the two-step process involves the general principle of applying a portion of the total sulfonated aromatic condensate composition to be applied in the standard dyebath with an appropriate amount of magnesium sulfate (magnesium sulfate, 0 to 0.35% on the weight of the fabric for each 1% on the weight of the fabric of the sulfonated aromatic condensate).
  • magnesium sulfate magnesium sulfate, 0 to 0.35% on the weight of the fabric for each 1% on the weight of the fabric of the sulfonated aromatic condensate.
  • the balance of the total sulfonated aromatic condensate composition (with 0 to 0.35% of magnesium sulfate) is then applied as an aftertreatment.
  • the amount of Epsom Salt required in both portions depends on the sulfonated aromatic condensate and the substrate being treated.
  • the dyebath composition is based on that typically used for continuous dyeing.
  • the appropriate amount of the sulfonated aromatic condensate composition (based on the optimum ratio and the total required for the particular substrate) is added to the dyebath.
  • a thiocyanate is added to the formulation used to treat the carpet fabric to overcome oxidative yellowing of the sulfonated aromatic condensate, and to provide the resulting carpet with better resistance of the dyes to strong oxidizing agents, such as ozone or the benzoyl peroxide found in commercial anti-acne preparations.
  • a salt containing a divalent cation is useful to improve exhaustion of the sulfonated aromatic condensate on high ICP polymer fibers.
  • a dispersing agent(s) is usually necessary in the formulation to prevent precipitation or coagulation due to incompatibility of the components of the formulation for treatment and/or the components with a fluorocarbon treated carpet fabric. Acids are used to buffer the formulations. It has been discovered that citric acid or any acid with a sequestering agent creates an additional improvement in yellowing characteristics of sulfonated aromatic condensate treated fiber or fabric.
  • Ammonium thiocyanate and sulfonated aromatic condensates exhaust onto nylon fibers under comparable application procedures.
  • the two products may be co-applied providing that the uptake of one material does not interfere with the other. Therefore, the selection of the sulfonated aromatic condensate is important.
  • Some sulfonated aromatic condensates exhaust preferentially over ammonium thiocyanate. But to the contrary there was a synergistic effect of Intratex N® (which is reported to be formaldehyde condensed with an alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone) and ammonium thiocyanate on benzoyl peroxide spotting resistance.
  • ammonium thiocyanate in the composition is as an antioxidant to prevent light induced yellowing of Intratex N®. This combination was found to give a sufficient improvement (acceptable light-fastness) for beck applications, but was insufficient for continuous applications (although improved).
  • a novel dispersant system using Tamol SN® and Monawet MB-45® was developed to prepare a stable composition containing Intratex N®, ammonium thiocyanate and citric acid in concentrated form for continuous applications.
  • a new dispersant system was developed to prepare a stable concentrate containing Intratex N® and ammonium thiocyanate for beck adjations.
  • Example Compositions Component Composition 1, % Solids, % Composition 2, % Solids, % Intratex N* (s.a.c.) - - 18.9 3.8 Intratex N-1* 25 5 - - Ammonium Thiocyanate 6.00 6 - - Citric Acid (50% solution) 14.30 7.15 - - Sulfuric Acid - - 1.11 1.1 Tamol SN (sodium salt of condensed naphthalene sulfonic acid) 4.00 3.9 7.32 7.1 Monawet MB-45 (di-isobutyl sulfosuccinate) 20.00 9 - - Epsom Salt 6.00 6 - - (Magnesium Sulfate) 24.7 2.9 Demineralized Water 33.03 0 72.65 0 * Same concentration of same s.a.c., N-1 has pH 7, N has pH 10.5.
  • Any thiocyanate such as those listed above is expected to be effective, although the copper, ferrous and ferric thiocyanates may have to be color compensated.
  • any agent that is effective can be used, such as for any process formulation, the condensed naphthalenic salts, the alkyl sulfosuccinates, a mixture of them, and for batch process systems salts of polymeric carboxylic acid, and polyethylene glycol ethers.
  • the polyphosphates such as sodium tripolyphosphate (STPP), aminocarboxylic acids, such as ethylenediamine tetraacetic acid (EDTA), hydroxy-carboxylic acids, such as tartaric and citric acid, and the aminoalcohols, such as triethanolamine (TEA) are expected to be effective.
  • STPP sodium tripolyphosphate
  • aminocarboxylic acids such as ethylenediamine tetraacetic acid (EDTA)
  • hydroxy-carboxylic acids such as tartaric and citric acid
  • aminoalcohols such as triethanolamine (TEA)
  • Composition 1 On a commercial dyeing range Composition 1 was applied both in a two-step (continuous-continuous) and in a continuous aftertreatment only process to a normal and to a high ICP fiber carpet fabric.
  • the normal fiber was in a 132 tex (1186 denier) Superba heat set textured yarn.
  • the high ICP fiber was a 189 tex (1700 denier) textured yarn which was heat set by a proprietary Pharr process with a high heat history giving an ICP of 3.92 compared to normal ICP of about 3.8.
  • Both fibers were previously treated with a spin finish containing a soil-release fluorocarbon as described in U.S.-A-4,604,316 and/or U.S.-A-4,192,754.
  • the fabric was dyed gray.
  • the prewash and treatment application was by spray just after the dryer but before the final wash on the continuous dye range. Following are the dyes and chemicals used in the continuous dyebath.
  • the two-step process with composition gives considerably better stain resistance than the aftertreatment (only) process, at equal total add-on levels. This shows potential for achieving acceptable performance at lower total add-on levels.
  • the two-step process also gives acceptable stain resistance on the "high ICP" substrate at levels comparable to that currently being used for s.a.c. normal substrates by aftertreatment only.
  • Stain resistnace improves and lightfastness is adversely effected (yellowing) as the Composition 1 concentration in the concurrent portion increases, with total add-on level constant. Acceptable yellowing and stain resistance was achieved at 4% on the weight of the fiber of Composition 1 in the concurrent portion.
  • H/S Superba heat set
  • Composition 1 on the high ICP fabric did not yield acceptable staining performance.
  • level of Composition 1 was increased from 11 to 15% owf on the high ICP fabric, stain resistance was further improved to a "Marginal" performance level (stain rating of 1.5 at 4- and 24-hour blot times).
  • the two-step process gave considerably better stain resistance than the aftertreatment only process on both substrates, at equal total application levels. No staining at 24 hours was obtained on the Superba H/S fabric using 4% on the weight of the fiber in the Dyebath and 7% on the weight of the fiber in the A/T. These same levels on the high ICP substrate gave staining performance equal to the Superba fabric aftertreated (only) with 11% an the weight of the fiber of Composition 1 (stain rating of 0.5 at 24 hours).
  • the two-step process gave only a slight reduction in the benzoyl peroxide spotting performance than the aftertreatment process, at equal add-on levels.
  • Composition 1 showed slightly more soiling when applied by aftertreatment, as the concentration applied was increased.
  • the fabrics treated were (a) a fabric tufted from a 132 tex (1186 denier) continuous filament textured medium dye fiber in a Superba heatset (H/S) yarn to a 0.79 Kg (28-ounce) cut pile fabric and (b) a textured 3.15/2 cotton count yarn from a 2.1 tex (19 denier) per filament staple deep dye fiber heat in a Suessen and tufted into 1.36 Kg (48-ounce) fabric. Both were pretreated with the fluorocarbon of Example 1 and were to be dyed light gray.
  • the nominal application conditions were 60°C (140°F) preheat water temperature, 81.2°C (180°F) application liquor temperature, 500 to 600% w.p.u. application liquor, the dyes and dyebath additives were as in Example 1, except no sequestrene was used. No Composition 2 or other s.a.c. was added to the dyebath.
  • the following Tables show the application conditions and results. TABLE XI REPELLENCY DATA (FINISHED CARPETS) Sample I.D. Nominal Comp.2 Applied, % Repellency Oil Water 1 0 4.0 4.0 2 15.0 4.0 4.5 3 0 3.0 4.0 4 9.0 3.0 4.5
  • This Example 2 demonstrates the effectiveness of the sulfonated aromatic condensate with only a dispersing agent and further demonstrates the effectiveness of the continuous aftertreatment process of this invention.
  • Example 2 demonstrates the effective use of the process of this invention on fabric which has not been previously treated with any fluorocarbon compound for antisoiling properties.
  • the Composition 2 used in the continuous aftertreatment process (no two step) of this invention as set forth in Example 1.
  • Dyebath formulation was as in Example 2.
  • Conditions were as in Example 1, more specifically, preheat water temperature was 195°F (90.6°C) at 100% w.p.u. to achieve carpet temperature of 135-140°F (57.2 to 60°C).
  • Aftertreatment liquor temperature was 180-185°F (82.2 to 85°C) to achieve carpet temperature of 160-170°F (71.1 to 76.7°C).
  • Aftertreatment dwell time was 30 seconds before washing at 40:1 liquor to fabric ratio, hydroextraction and drying.
  • Example 3 Part 1
  • Composition 1 was used with the results shown in the following tables. All fabric was without fluorocarbon treatments.
  • Example 4 The process on the fabric of Example 4 was repeated, also using Composition 2 with and without the Tamol dispersant, and also adding NH4SCN to show its benefits.
  • Composition 2 tended to exhibit better staining performance than Intratex N® alone at comparable levels. The differences between the two diminish as the overall concentration increases.
  • Intratex N® and Tamol SN® (by themselves) were found to behave differently when exposed to light. Intratex N® yellows/browns severely at short light exposures (20 afu). This yellowing or browning then fades as the lightfastness exposure is continued. Tamol, on the other hand, greens when exposed to 20 afu and upon continued exposure the green fades to yellow. The overall rating of the shade change does not necessarily improve from the 20 to 40 afu exposures. The severity of shade change is about equal for Intratex N® and Tamol SN®.
  • Composition 2 The break of Composition 2 at short lightfastness exposures (20 afu) appears as a hybrid of Intratex N® and Tamol SN® alone (at the respective levels in Composition 2).
  • Yellowing diminishes as the NH4SCN level increases. The yellowing is significantly reduced using approximately 0.3% owf NH4SCN for every 1.0% owf Intratex N.
  • Tamol SN® was found to be unaffected by exposure to NO2, while Composition 2 and Intratex N® yellowed severely.
  • the addition of NH4SCN improved NO2 yellowing only slightly, but not enough to raise Grey Scale ratings above 1-2.
  • Intratex N® had a significant impact on ozonefastness, both alone and as Composition 2. While overall fastness ratings tended to be better at extended cycles compared to the nontreated control, a significant yellowing occurs.
  • Intratex N® overwhelms any improvement achieved by the addition of NH4SCN.
  • Samples incorporating NH4SCN tend to yellow less when exposed to ozone and higher levels yield more improvement.
  • the significant improvement in ozonefastness of NH4SCN alone was not achieved, but were improved over nontreated samples.
  • Table XXIV shows the benzoyl peroxide performance identical when 0.3% owf NH4SCN is applied with either Composition 2 or s.a.c. at several levels.
  • Benzoyl peroxide spotting improves as the NH4SCN concentration is increased from 0.3 to 0.6% owf. The improvement becomes more noticeable at the highest benzoyl peroxide concentration and probably beyond.
  • the dispersant, Tamol SN® contributes to the light induced yellowing of Composition 2 but is not the sole cause. Elimination of Tamol SN® from Composition 2 would not significantly improve or resolve yellowing on Superba H/S substrates. The elimination of Tamol SN® could reduce staining performance slightly at lower add-on's and increase the foaming of the treatment liquor upon spray application.
  • Intratex N® is the sole cause of yellowing upon exposure to NO2 of Composition 2.
  • Tamol does not interfere with any of the NH4SCN benefits.
  • Intratex N® has a significant impact on ozonefastness (yellows) and overwhelms the ozonefastness improvement benefits of NH4SCN. There is, however, a reduction in the yellowing and an improvement over Composition 2 alone at a nominal 0.6% owf NH4SCN.
  • NH4SCN has no adverse impacts on Composition 2 stain blocking benefits.
  • Benzoyl peroxide spotting performance may be further improved, particularly at higher benzoyl peroxide concentrations, by increasing the NH4SCN level to 0.6% owf. TABLE XXII STAINING PERFORMANCE DATA Sample I.D.
  • This example demonstrates the two-step, batch-batch (beck-beck) process technique.
  • prior art has shown that application of sulfonated aromatic condensates (stain blockers) to nylon improves resistance to staining by most food colors.
  • the preferred mode of application has been a low temperature (48.9 to 82.2°C (120 to 180°F) treatment with the stain blocker after dyeing has been completed.
  • prior art includes application of stain blockers concurrent with dye application. This invention embodies application of a portion of the total stain blocker concurrently with dye application, and application of the remainder in a low temperature aftertreatment step. (two-step process).
  • the two-step process results in a level of stain performance superior to that which is achieved by the prior art at the same total add-on concentration of stain blocker.
  • use of ammonium thiocyanate in the aftertreatment step improves dye fastness to ozone, benzoyl peroxide (acne medications) and light.
  • This example shows that two-step process is superior to either concurrent or aftertreatment.
  • the total was distributed between dyebath and aftertreatment in the following ways: Dyebath, % Aftertreatment, % 0 100 50 50 100 0
  • This example shows use of ammonium thiocyanate in two-step process for improved resistance to benzoyl peroxide and light fading.
  • Intratex N was applied using the 50%/50% two-step mode.
  • a second sample was prepared in the same way but an Intratex N pre-formulated mixture containing ammonium thiocyanate (Composition 3) was used in the aftertreatment step.
  • Composition 3 is 40% Intratex N-l, 12% ammonium thiocyanate, 21.5% Monawet MB45, 26.5% Water.
  • the total was distributed between dyebath and aftertreatment in the following ways: Dyebath, % Aftertreatment, % 0 100 5 95 10 90 20 80 30 70 50 50
  • Dyed carpet fiber especially that made from nylon, whether or not it is treated with a sulfonated aromatic condensate or other treatments, is susceptible to significant color fading due to exposure to ozone, benzoyl peroxide and products containing chlorine.
  • the problem was lessened to some extent when the dye industry changed over to acid dyes from disperse dyes. Acid dyes were less able to migrate and be destroyed by ozone because they were electronically bound to the nylon. However, the use of acid dyes did not eliminate these color fastness problems.
  • antioxidants and antiozonants available on the market. These products are usually aromatic and contain amine or sulfur functionalities. These products have several disadvantages: aromatics usually yellow the fiber upon further heat treatment, and the amines and sulfur functionalities cause a reduction in nylon lightfastness. Also, these chemistries probably act as sacrificial agents and it has been difficult to apply enough onto the fiber to have long term benefit.
  • the thiocyanates such as ammonium thiocyanate, are antiozonants that are well known.
  • the cation of the thiocyanate may be ammonium, sodium, potassium, zinc, copper, ferrous, ferric, methyl or phenyl. They had the additional advantage over the other antioxidants in that they do not reduce lightfastness. However, it has not been economically possible to apply enough of the thiocyanate during dyeing to have long term effectiveness as it is also a sacrificial agent. (Ammonium thiocyanate also appears to aglomerate the dye molecules which also improves ozone fastness.)
  • the amounts added introduced an equivalent quantity of thiocyanate concentration onto the fiber.
  • ammonium, sodium and potassium thiocyanates were all equally superior to untreated nylon in resistance to ozone, benzoyl peroxide and chlorine bleach fastness.
  • the other 15 thiocyanates were slightly more resistant to these color fade tests than the untreated nylon.
  • the xenon lightfastness of all the samples were similar to untreated nylon except CuSCN which was more resistant and the phenyl-based thiocyanate which was much worse.
  • pH 2 temperature was varied to achieve the following exhaustion levels. Temperature, Exhaustion, % °F ( °C) 75 23.9 70 100 37.8 66 120 48.9 63 140 60.0 60 180 82.2 75 200 93.3 98 Thus by raising the temperature, it is expected that more complete exhaustion can be achieved at higher pH levels.

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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)
  • Coloring (AREA)
  • Carpets (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (14)

  1. Verfahren zum Aufbrauchen eines wasserlöslichen Thiocyanates auf eine Polyamidfaser, wenn die Faser mit dem Thiocyanat in Kontakt gebracht wird, dadurch gekennzeichnet, daß das Kontaktieren bei einem pH-Wert zwischen 1 und 5 durchgeführt wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Thiocyanat Ammonium-, Natrium-, Kalium- oder Zink-Thiocyanat ist.
  3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der pH-Wert zwischen 1 und 4 liegt.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß während des Kontaktierens zwischen 0,1 und 12% des Fasergewichtes an Thiocyanat vorhanden ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Thiocyanat mit der Faser in einem Farbbad in Kontakt gebracht wird.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Thiocyanat mit der Faser nach dem Färben der Faser in Kontakt gebracht wird.
  7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Faser einen Fluorkohlenstoff zum Verbessern der Verschmutzungseigenschaften der Faser aufweist und ein sulfoniertes aromatisches Kondensat entweder an der Faser vorhanden ist oder gemeinsam mit dem Thiocyanat aufgebracht wird.
  8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß der Fluorkohlenstoff eine Perfluoralkyl-Radikale enthält und das sulfonierte aromatische Kondensat durch Kondensation von Formaldehyd mit einem oder mehreren Phenol(en) gebildet ist.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß der Fluorkohlenstoff ein Gemisch von durch zwei Reaktionen gebildeten Oligomeren ist, nämlich erstens der Reaktion von Pyromellitsäure-Dianhydrid mit einem fluorierten Alkohol, und zweitens wird das Reaktionsprodukt weiters mit Epichlorhydrin umgesetzt, und daß das Kondensat mit einem Alkalisalz von para-Phenolsulfonsäure und mit 4,4'-Diphenolsulfon formaldehydkondensiert wird.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß während des Kontaktierens zwischen 0,1 und 12% Thiocyanat, basierend auf dem Gewicht der Faser, und zwischen 0,05 und 0,4% Fluorkohlenstoff, basierend auf dem Gewicht der Faser, vorhanden sind.
  11. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß ein wäßriges sulfoniertes aromatisches Kondensat auch zum Kontaktieren der Polyamidfaser verwendet wird.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß der Anteil an verwendetem sulfonierten aromatischen Kondensat zwischen 0,25 und 0,40 Gramm Feststoff des Kondensats pro Liter der wäßrigen Lösung aufweist.
  13. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das sulfonierte aromatische Kondensat durch Kondensation von Formaldehyd mit einem oder mehreren dihydroxy-aromatischen Diphenolsulfon(en) gebildet ist.
  14. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das Kondensat mit einem Alkalimetallsalz von para-Phenolsulfonsäure und mit 4,4'-Diphenolsulfon formaldehydkondensiert ist.
EP88904055A 1987-09-28 1988-04-06 Verfahren zum erhöhen der fleckenbeständigkeit von teppichfasern Expired - Lifetime EP0382724B1 (de)

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US5118551A (en) * 1990-03-27 1992-06-02 Allied-Signal Inc. Method to impart stain resistance to polyamide textile substrates
US5135774A (en) * 1990-03-27 1992-08-04 Allied-Signal Inc. Method to impart coffee stain resistance to polyamide fibers
US5670246A (en) * 1995-09-22 1997-09-23 E. I. Du Pont De Nemours And Company Treatment of polyamide materials with partial fluoroesters or fluorothioesters of maleic acid polymers and sulfonated aromatic condensates
US6852134B2 (en) 1999-07-08 2005-02-08 Invista North America S.A.R.L. Method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby
US7491805B2 (en) 2001-05-18 2009-02-17 Sirna Therapeutics, Inc. Conjugates and compositions for cellular delivery
US6811574B2 (en) 2000-07-03 2004-11-02 Dupont Textiles & Interiors, Inc. Method of after-treatment of a dyeable nylon textile surface with a stain resist and the article produced thereby
US6814758B1 (en) * 2001-04-26 2004-11-09 Simco Holding Corporation Process for protecting dyed nylon fibers from colorants and chemical agents

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US3039981A (en) * 1955-12-27 1962-06-19 Owens Corning Fiberglass Corp Aqueous binder composition of phenolformaldehyde condensate, aluminum sulfate and mineral oil, and glass fiber coated therewith
BE759823A (fr) * 1969-12-03 1971-05-17 Bayer Ag Agents ameliorant la solidite au mouille
CA1264505A (en) * 1986-02-14 1990-01-23 E.I. Du Pont De Nemours And Company Method for producing stain resistant polyamide fibers
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