EP0382724A1 - Method to enhance stain resistance of carpet fibers. - Google Patents
Method to enhance stain resistance of carpet fibers.Info
- Publication number
- EP0382724A1 EP0382724A1 EP88904055A EP88904055A EP0382724A1 EP 0382724 A1 EP0382724 A1 EP 0382724A1 EP 88904055 A EP88904055 A EP 88904055A EP 88904055 A EP88904055 A EP 88904055A EP 0382724 A1 EP0382724 A1 EP 0382724A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- effective amount
- carpet
- fabric
- sulfonated aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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- 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 improved methods and compositions to enhance stain resistance of carpet fibers.
- Sulfonated aromatic condensates alone in a new process or in combination with other compounds are used to improve stain resistance.
- Related technology is disclosed in commonly assigned, copending applications Serial No. 889,705 filed July 28, 1986, on sulfonated benzotriazoles and Serial No. 074,487 filed July 23, 1987, on sulfonated aromatic formaldehyde condensates, such as diphenyl ether condensates.
- sulfonated aromatic condensate is meant 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 is meant 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 -£C-N_- structure along with
- 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 5 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 5 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, 0 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 ⁇ T 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 X3 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 Encyclo- 5 pedia 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.
- 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 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.
- This invention is several interrelated embodiments wherein the several new s.a.c. application formulations are used in the several new application processes.
- First described is a continuous aftertreatment for dyed nylon carpet fabric, using several combinations of chemical compositions to apply a s.a.c.
- the two- step process of treating carpet fabric with a s.a.c, still using the continuous aftertreatment as the second step is described.
- This includes batch (or beck)-continuous and continuous-continuous two-step treatment.
- the combination of s.a.c. and the thiocyanates, and with various added chemicals, to improve resistance of dye and s.a.c. on the fiber to oxidation is next described.
- the first embodiment of this invention is a method to continuously treat dyed nylon carpet fabric to impart improved resistance to staining comprising preheating the dyed carpet fabric with water at a temperature of between about 140 and 212°F (60 and 100°C) to a wet pick-up of above about 75% by weight, and a carpet temperature of between about 130 and 210°F (54.4 and 99°C), then extracting the water from the carpet fabric to a wet pick-up of between about 30 to 190% by weight, then applying an aqueous solution of an effective amount of a sulfonated aromatic condensate to the carpet fabric at a pH of between about 1.5 to 5.5, at a concentration of between about 0.25 and 40 grams of solids of said condensate per liter of aqueous solution, at a wet pick-up between 200 and 650% by weight, an aqueous solution liquor of between about 140 and 212°F (60 and 100°C) to achieve a carpet fabric temperature between about 130 and 210°F (54.4 and 99
- 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 about 0.25 and 10 grams per liter of aqueous solution.
- the preferred wet pick-up of the aqueous solution is between about 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 mimimur ⁇ is 400%.
- the carpet fabric be held in the aqueous solution for between about 2 and 30 seconds.
- the preferred wet pick-up after extracting is between about 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 con ⁇ densed 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 about 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 dianhydri.de 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 may 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, a 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, ' -diphenol- sulfone., 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 about 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 about 0.05 and 0.8% on the weight of the fabric
- the ammonium thiocyanate can be present in an amount in about 0.03 to 1% on the weight of the fabric
- the sulfonated aromatic condensate can be present in an amount of between about 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 about 0 and 3 parts by weight to parts by weight of the sulfonated aromatic condensate.
- the preferred amounts of the compounds are about 0.05 and 0.4% by weight of the fabric of the fluorocarbon, between about 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 about 0.15 and 1.5% on. the weight of the fabric of the * ?
- 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 after ⁇ treatment 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 exhausts onto the fiber at the possibly higher pH and so that the .stain resistance of the nylon fiber in the carpet fabric, especially an easily dyed nylon fiber having a high index of crystalline perfection and having a very open internal crystal polymer structure, is enhanced and durability steam cleaning of the stain resistance is enhanced, or the effective amount of sulfonated aromatic condensate is lower to achieve the same level of stain resistance.
- 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 between about 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 about 0.05 and 10% on weight of the fiber of t e , sulfonated aromatic condensate, between about 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 5 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
- the sulfonated aromatic condensate can be a condensate with formaldehyde, can further be formed by the condensation of formaldehyde wit '
- 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 0 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 10 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 5 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.
- a method of improving light induced yellowing of stain resistant nylon in fiber treated with an effective amount of sulfonated aromatic condensate from an aqueous solution comprises using an effective amount of citric acid or any acid with a sequestering agent to buffer the aqueous solution containing the sulfonated aromatic condensate for treating the fiber at a pH between about 1 and 5.5.
- 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 110 and 195°F (60 and 91°C) 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 about 10:1 to 100:1 at a temperature of 158 to 212°F (70 to 100°C) for 15 to 90 minutes.
- Preferred conditions for the second step are a liquor to fabric ratio of about 10:1 to 100:1 for a period of about 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 present in an amount of from about 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 can also contain an effective amount of a thiocyanate such as ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl thiocyanate.
- 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
- the more preferred amounts are where the fluorocarbon is present in an amount of between about 0.05 and p.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.
- a method of improving exhaustion of a water soluble thiocyanate onto polyamide fiber comprising contacting the fiber with an effective amount of the thiocyanate at a pH between about 1 and 5 wherein 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, is disclosed.
- 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 about 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 about 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.
- a fluorocarbon to inhibit soiling of the fiber
- 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 about 0.1 and 12% thiocyanate on the weight of the fiber and between about 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 5 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 continuous aftertreatment process of this invention has the following advantages over the known prior art processes:
- the process is also applicable to continuously aftertreating piece" (or beck) dyed goods at the wet goods dryer.
- the process involves the general principle of
- 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).
- 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 a 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 of this invention may be carried out on the previously existing equipment.
- this invention provides an economical and effective means to apply sulfonated aromatic formaldehyde condensates to impart stain resistance to dyed carpets.
- the process is applicable to over 90% of all carpets treated with sulfonated aromatic formaldehyde condensates.
- the continuous aftertreatment embodiment 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 (fiber) 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.
- 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) .
- 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 sulfonated aromatic condensate In addition to a sulfonated aromatic condensate other chemical compounds such as a thiocyanate are 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. Also 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.
- 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) .
- composition Solids Composition Solids, Composition Solids, Com onent 1, % % 2,
- composition Solids Composition Solids, Composition Solids, Component 1, % % 2, % %
- Any thiocyanate such as those listed in the Summary of the Invention 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
- TAA triethanolamine
- Example 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 an 1186 denier Superba heat set textured yarn.
- the high ICP fiber was a 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. 4,604,316 and/or U.S. 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. Control:
- Chemcogen DCG is sulfonated alkyl diphenylether - 30-38% active.
- Defoamer AC is a proprietary defoamer from Fuller Sales.
- Sequestrene 30A is ethylene diamine tetraacetic acid.
- 1 and 2 are a controls.
- Both fabrics are 40. oz/sq yd cut piles.
- A/T Liq ⁇ or Temperature ranged from 180-182°F (82.2-83.3°C) .
- Line speed for both fabrics was 30 ft/min.
- Af ertreatment pH was always between 2.8 and 3.0 except controlfas 7.6. gallons per minute
- Line speed for both fabrics was 30 ft/min.
- Detergent solution 1 oz./gal. ALL-IN-ONE (Certified Chemical & Equipment, Cleveland, OH). 1 See Example 6, ' Part 2, Stamm "Performance", "Drop Test”.
- Numbers in parentheses represents surface tension of the test fluids.
- 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.
- 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) .
- AFU on any of the trials conducted, but begn to be noticed at 40 AFU.
- Composition 1 showed slightly more soiling when applied by aftertreatment, as the concentration " applied was increased. With total add-on constant, the two-step process had less impact on soiling than aftertreatment alone.
- composition 1 has low pH. Use in the dyebath will result in pH's of 3.0-3.5, requiring an alkalai to adjust pH.
- composition 1 Concentration:
- Example 2 This is a further example of the continuous aftertreatment process of the invention, using Composition 2 in the treatment of the carpet fabric.
- the fabrics treated were (a) a fabric tufted from an 1186 denier continuous filament textured medium dye fiber in a Superba heatset (H/S) yarn to a 23-ounce cut pile fabric and (b) a textured 3.15/2 cotton count yarn from a 19 denier per filament staple deep dye fiber heat in a Suessen and tufted into 48-ounce fabric. Both were pretreated with the fluorocarbon of Example 1 and were to be dyed light gray.
- the nominal application conditions were 140°F (60°C) preheat water temperature, 180°F (81.2°C) 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.
- Preheat liquor temperature was 140°F (60°C).
- Carpet temperature was 127-130°F (52.8-54.4°C) .
- Application liquor temperature was 179-182°F (81.7-83.5°C) and carpet temperature was 156-161°F (68.9-71.7°C) .
- - - TABLE VII CONTINUED
- Preheat liquor temperature was 140°F (60°C).
- Carpet temperature was 127-130°F (52.8-54.4°C) .
- Application liquor temperature was 179-182°F (81.2-83.3°C) and carpet temperature was 156-161°F (68.9-71.7°C) .
- 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 3 - Part 1
- Dyebath formulation was as in Example 2.
- 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 C) to achieve carpet temperature of 160-170°F (71.1 to 76.7°C).
- Samples 2 and 4 were applied at pH 3. Samples 1 and 3 were applied at pH 2. * Extracted from carpets with 0.IN NaOH for four hours and analyzed by HPLC against original material.
- Example 3 - Part 2 The conditions of Example 3 - Part 1 were repeated except Composition 1 was used with the results shown in the following tables. All fabric was without fluorocarbon treatments. 1.0
- Example 4 The process and conditions of dyeing formulations of Example 2 using Composition 2 were repeated with and without citric acid to adjust pH in the continuous aftertreatment application process of this invention the fabric was in 32 ounce per square yard cut pile construction of a 1185 denier bulked continuous filament, Superba H/S, Sick-dyed grey. The fiber had been treated with fluorocarbon for antisoiling properties. Also all dispersing agents (Tamol) were omitted from Composition 2 for another set of samples. Epsom salt (49% MgS ⁇ 4) was added to another set of samples. Citric acid was used as a rinse and in the application liquor. Use of citric acid in the treatment liquor or to adjust pH resulted in improved yellowing of the sulfonated aromatic condensate treated fiber. The combination of Epsom salt and citric acid further reduced the tendency to yellow whether due to exposure to ozone or to N ⁇ 2 « The following tables provide application conditions and results. -42-
- carpet temperature before A/T ranged from 132 to 138°F (55.6-58.9°C) .
- A/T liquor temperature was 183 to 185°F (83.9-85°C) .
- Tamol dispersant and also adding NH4SCN to show its " benefits.
- 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 continu'ed. 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.
- 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 level»s yield more improvement.
- the significant improvement in ozonefastness of NH4SCN alone was not achieved, but were improved over nontreated samples.
- NH4SCN is applied with either Composition 2 or s.a.c at several levels.
- the dispersant, Tamol SN contributes to the light induced yellowing of Composition 2 but is not the -49- 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.
- carpet temperature before A/T ranged fro i ⁇ 132 to 144°F (55.6-62.2°C) .
- ammonium thiocyanate in the aftertreatment step improves dye fastness to ozone, benzoyl peroxide (acne medications) and light.
- Example 6 Part 1 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:
- Varying amounts of Magnesium Sulfate were used (0% owf to 4% owf) .
- 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. 1 Registered m of General Foods Corporation. -57- Performance:
- Example 6 Part 3 This example shows that 50%/50% two-step mode is preferred and the 2% magnesium sulfate is optimum.
- the total was distributed between dyebath and aftertreatment in the following ways:
- Reference samples 2 through 23 Table XXIX. Using the test protocols from Example 1, samples 20 through 23 (50%/50% application mode) have best stain resistance. Sample 20 is best of group (uses 2% and 2% owf magnesium sulfate) . -58-
- Example 7 This example describes use of a sequestering agent in the continuous aftertreatment process of this invention.
- the general procedure was as in Example 2.
- Calquest ADP Mfrs. Chem. ) added to treatment bath containing Comp. 2 at levels corresponding to 0.5 and 1.0% owf.
- Prewet/heat carpet at 195°F (90.6°C) and 100% w.p.u. to achieve a carpet temperature prior to treatment of 135 to 140°F (57.2 to 60°C) .
- Apply A/T liquor at 400% w.p.u. and 175 to 180°F.
- the change in the dyed shade was reduced (went more to the blue side) when the sequestering agent was used.
- Light induced yellowing was improved between 1/2 to 1 gray scale unit at 20 AFU using the sequestering agent. No further improvement was noted going from the low to the high concentration. There also appeared to be more of an improvement (or fading) of the yellowing in going from 20 to 40 AFU's when the sequestering agent was included.
- sequestering agent in the Composition 2 formulation shows reduced yellowing at low lightfastness exposures and upon exposure to ozone.
- sequestering agents would also be useful, for example, the polyphosphates, such as Calgon which is sodium hexametaphosphate, aminocarboxylic acids, such as EDTA or ethylenediaminetetraacetic acid, the amino alcohols, and the hydroxycarboxylic acids, including citric acid.
- 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. -69-
- 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.
- the amounts added introduced an equivalent quantity of thiocyanate concentration onto the fiber.
- pH 2 temperature was varied to achieve the following exhaustion levels.
- Limitation Variation Reason preheat water temp below less uniform application 140 °F ( 60 ° C) and carpet during the following treat ⁇ temp , below 130 °F ( 54.4°C) ment and less effective or economic to heat carpet preheat water temp, above atmospheric process, water 212°F (100°C) and carpet cannot be heated above the above 210°F ( °C) boiling point less than 75% w.p.u. less uniform, poor preheat step penetration extracting to less than less uniform, poor 30% w.p.u. penetration extracting to above 190% dilutes following appli ⁇ w.p.u. cation liquor, less effective application pH below 1.5 corrosive application pH above 5.5 less effective, due to compounds of aqueous soln.
- Limitation Variation Reason second step pH below 1.5 corrosive second step pH above 5.5 less effective, due to compounds of aqueous soln. penetrating too deep into fiber, at very high pH no exhaustion of compositions second step temp. below uneconomical, takes too 110°F ( °C) long second step temp, above less effective, due to 195°F. ( °C) compounds of aqueous soln.
- first & second step liquor less uniform, poor wetting fabric ratio below 10 and penetration first & second step liquor: uneconomical fabric ratio above 100 first step temp, below uneconomical, nonuniform 158°F (70°C) application, takes too long first step temp, above atmospheric process, water 212°F (100°C) cannot be heated above the boil first step treating time blotches and streaks, less than 15 minutes nonuniform first step treating time uneconomical over 90 minutes second step treating time nonuniform application under 5 minutes less than 0.05% owf fluoro ⁇ does not provide anti- carbon on pretreated fabric soiling effect over 0.4% owf fluorocarbon uneconomical on pretreated fabric - - Limitation Variation Reason below 0.25% owf MgS04 ineffective over 4% owf MgS04 poor lightfastness, uneconomical, poor dyeing, shade changes below 0.03% owf NH4SCN ineffective above 1% owf NH4SCN uneconomical below 0.15%
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US10165287A | 1987-09-28 | 1987-09-28 | |
US101652 | 1987-09-28 | ||
PCT/US1988/001112 WO1989002949A1 (en) | 1987-09-28 | 1988-04-06 | Method to enhance stain resistance of carpet fibers |
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EP0382724A1 true EP0382724A1 (en) | 1990-08-22 |
EP0382724B1 EP0382724B1 (en) | 1995-02-22 |
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EP88904055A Expired - Lifetime EP0382724B1 (en) | 1987-09-28 | 1988-04-06 | Method to enhance stain resistance of carpet fibers |
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EP (1) | EP0382724B1 (en) |
JP (1) | JPH03500307A (en) |
AT (1) | ATE118837T1 (en) |
CA (1) | CA1330476C (en) |
DE (1) | DE3853165T2 (en) |
WO (1) | WO1989002949A1 (en) |
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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 (en) * | 1969-12-03 | 1971-05-17 | Bayer Ag | AGENTS IMPROVING WET SOLIDITY |
CA1264505A (en) * | 1986-02-14 | 1990-01-23 | E.I. Du Pont De Nemours And Company | Method for producing stain resistant polyamide fibers |
DE3683151D1 (en) * | 1986-03-06 | 1992-02-06 | Monsanto Co | Stain-resistant NYLON FIBERS. |
-
1988
- 1988-04-06 DE DE3853165T patent/DE3853165T2/en not_active Expired - Fee Related
- 1988-04-06 WO PCT/US1988/001112 patent/WO1989002949A1/en active IP Right Grant
- 1988-04-06 EP EP88904055A patent/EP0382724B1/en not_active Expired - Lifetime
- 1988-04-06 JP JP63503627A patent/JPH03500307A/en active Pending
- 1988-04-06 AT AT88904055T patent/ATE118837T1/en not_active IP Right Cessation
- 1988-09-22 CA CA000578108A patent/CA1330476C/en not_active Expired - Fee Related
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ATE118837T1 (en) | 1995-03-15 |
WO1989002949A1 (en) | 1989-04-06 |
DE3853165D1 (en) | 1995-03-30 |
JPH03500307A (en) | 1991-01-24 |
CA1330476C (en) | 1994-07-05 |
DE3853165T2 (en) | 1995-07-27 |
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