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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
• • 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
  • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
  • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
• • 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
• • 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
• • 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

• the present invention relates to stain-­resistant compositions comprising sulfonated phenol-­formaldehyde condensation products and polymers of ethylenically unsaturated aromatic monomers, polyamide textile substrates treated with the same, and processes for their preparation.
• the stain-resistant compositions and substrates of this invention possess stain resistance that is as good as or better than previously known compositions and substrates but do not suffer from yellowing to the extent that previously known materials do.
• Polyamide substrates such as carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages.
• An especially troublesome staining agent is FD&C Red Dye No. 40, commonly found in soft drink preparations.
• Different types of treatments have been proposed to deal with staining problems.
• One approach is to apply a highly fluorinated polymer to the substrate.
• Another is to use a composition containing a sulfonated phenol-formaldehyde condensation product.
• Liss and Beck in U.S. Patent Application Serial No. 124, 866, filed 23 November 1987, disclose stain-resistant synthetic polyamide textile substrates having modified sulfonated phenol-­ formaldehyde polymeric condensation products deposited on them.
• Frickenhaus et al. in U.S. Patent 3,790,344, disclose a process for improving fastness to wet processing of dyeings of synthetic polyamide textile materials with anionic or cationic dye stuffs. After dyeing the textile materials, Frickenhaus et al. treated the dyed materials with condensation products prepared from 4,4′-dioxydiphenylsulphon, formaldehyde and either a phenol sulfonic acid, a naphthalene sulfonic acid, sodium sulfite or sodium hydrogen sulfite.
• Meister et al. in U.K. Patent Specification 1 291 784, disclose condensation products of 4,4′-dihydroxydiphenylsulphone, diarylether sulphonic acids and formaldehyde, and the use of such condensation products as tanning agents and as agents for improving the fastness to wet processing of dyeings obtained on synthetic polyamides with anionic and/or cationic dyestuffs.
• Meister et al. disclose that by preparing their condensation products in an acid pH range, leathers tanned with the condensation products showed practically no yellowing after 100 hours exposure to light in Xenotest apparatus.
• Allen et al. in U.S. Patent 3,835,071, disclose rug shampoo compositions which upon drying leave very brittle, non-tacky residues which are easily removed when dry.
• the compositions comprise water-­soluble metal, ammonium or amine salt of a styrene-­maleic anhydride copolymer, or its half ester, and a detergent.
• Water-soluble metal salts of Group II and the alkali metals (particularly magnesium and sodium) are preferred, and ammonium salts are most preferred by Allen et al.
• the present invention provides compositions containing a sulfonated phenol-formaldehyde condensation product and a hydrolyzed polymer of maleic anhydride and one or more ethylenically unsaturated aromatic monomers, polyamide textile substrates treated with such compositions so as to impart stain resistance to the substrates, and methods for imparting stain resistance to textile substrates by use of the compositions of this invention.
• compositions of the present invention are effective over a wide range of proportions of the modified polymeric sulfonated phenol-formaldehyde condensation products and the hydrolyzed polymers of maleic anhydride and ethylenically unsaturated aromatic monomers.
• a useful ratio is one in the range between about 5 and 70 percent by weight of said condensation product and between about 95 and 30 percent by weight of said maleic anhydride polymer.
• Preferably the ratio is in the range between about 10 and 60 percent by weight of said polymeric condensation product and between 90 and 40 percent by weight of said maleic anhydride polymer.
• the composition most preferably contains about 15 weight percent of said condensation product and about 85 weight percent of said maleic anhydride polymer.
• a composition containing about 90 to 70 weight of said maleic anhydride polymer and about 10 to 30 weight percent of said condensation product is most preferred.
• a composition containing about 50 weight percent of both said condensation product and said maleic anhydride polymer is most preferred.
• such a shampoo formulation is preferred for maintaining stainblocking performance of carpeting after trafficking in commercial establishments.
• the compositions of this invention exhibit less initial discoloration and better light-fastness.
• the compositions of this invention provide better stain resistance than do their individual components at equivalent levels of treatment, based on the weight of the textile substrate being treated.
• polymeric sulfonated phenol-formaldehyde condensation products which can be used for the purposes of this invention are any of those described in the prior art as being useful as dye-resist agents or dye-fixing agents, in other words, dye-reserving agents or agents which improve wetfastness of dyeings on polyamide fibers. See for example the Blyth et al., Ucci et al., Frickenhaus et al. and Meister et al. patents cited above.
• condensation products suitable for the invention are the MESITOL NBS product of Mobay Chemical Corporation (a condensation product prepared from bis(4-hydroxyphenyl)-sulfone, formaldehyde, and phenol sulfonic acid; U.S. Patent No. 3,790,344), as well as Erional NW (formed by condensing a mixture of naphthalene monosulfonic acid, bis(hydroxyphenyl) sulfone and formaldehyde; U.S. Patent No. 3,716,393).
• the condensation products are those disclosed by Marshall and by Liss and Beck in their patent applications described above, the contents of which are incorporated herein by reference.
• the modified sulfonated polymeric phenol-formaldehyde condensation products comprise one in which between about 10 to 25% of the polymer units thereof contain SO3( ⁇ ) radicals, and about 90 to 75% of the polymer units contain sulfone radicals.
• hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic monomers suitable for the purposes of this invention and their preparation are those described in our E.P.A. (inventors: Fitzgerald, Rao, Vinod, Henry and Prowse) Application Serial No. (Attorney Docket No. CH1458A), filed of even date herewith, the contents of which are incorporated herein by reference.
• Those polymers contain between about one and two polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride (hydrolyzed polymers containing three ethylenically unsaturated aromatic polymer units per maleic anhydride polymer unit are not suitable).
• Hydrolyzed polymers containing about one polymer unit derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride are most effective in imparting stain resistance to textile substrates.
• a variety of ethylenically unsaturated aromatic compounds can be used for the purpose of preparing the hydrolized polymers of this invention. They can be represented by the formula
• ethylenically unsaturated aromatic compounds suitable for the purposes of this invention include styrene, alpha-methylstyrene, 4-methyl styrene, stilbene, 4-acetoxystilbene (used to prepare a hydrolized 4-hydroxystilbene/maleic anhydride polymer), eugenol, isoeugenol, 4-allylphenol, safrole, mixtures of the same, and the like. From the standpoint of cost-effectiveness, a copolymer prepared from styrene and maleic anhydride at a 1:1 molar ratio is preferred.
• the hydrolyzed polymers can have molcular weights (number average) in the range between about 500 and 4000, preferably between about 800 and 2000. They are readily soluble, even at high concentrations, in water at neutral to alkaline pH; increasing dilution is needed at a pH below 6. they are also soluble in lower alcohols, such as methanol, and are somewhat soluble in acetic acid.
• compositions of this invention can be applied to dyed or undyed textile substrates. They can be applied to such substrates in the absence of a polyfluoroorganic oil-, water-, and/or soil-repellent materials. Alternatively, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the composition of this invention to it.
• the compositions of this invention can be applied to textile substrates in a variety of ways, e.g. during conventional beck and continuous dyeing procedures.
• the quantities of the polymers of this invention which are applied to the textile substrate are amounts effective in imparting stain-­resistance to the substrate.
• the amounts can be varied widely; in general, between about 0.1 and 2% by weight of them based on the weight of the textile substrate, usually about 0.6% by weight or less.
• the compositions can be applied, as is common in the art, at pHs ranging between 4 and 5. However, more effective exhaust deposition can be obtained at a pH as low as 2. More effective stainblocking is obtained if the compositions of this invention are applied to the textile substrate at higher temperatures. For example, at pH 2, 170°F is preferred, and 200°F is preferred at pH 5. However, stainblocking can be obtained when application is effected at room temperature, or even at that of cold tap water (10-15°C).
• compositions of this invention are applied in-place to carpeting which has already been installed in a dwelling place, office or other locale.
• the compositions can be applied as a simple aqueous preparation or in the form of an aqueous shampoo preparation with or without one or more polyfluoro­organic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described above, at temperatures described, and at a pH between about 1 and 12, preferably between about 2 and 9.
• stain-resists to carpeting is carried out in a Launder-O-Meter automated dyeing machine.
• One carpet piece is contained in each of several (up to twenty) stainless steel, screw-cap canisters.
• the canisters are held in a rack that rotates in a water bath whose temperature is automatically controlled for rate of heating, time at temperature and cooling.
• For a typical application bath one uses a 20 to 1 liquor to goods ratio with 2.5 weight % of the stain-resistant composition.
• the stain-resistant compositions can be applied at pH 2 or pH 5. At pH 2, an excess of sulfamic acid is used.
• an excess of ammonium sulfate is used, as well as 3g/L of magnesium sulfate and 1g/L of an alkyl aryl sulfonate (Alkanol® ND) or a suitable leveling agent.
• a solution of the stain-­resist composition is added to the Launder-o-Meter canister.
• the carpet sample to be treated is then placed in the canister, tufted side out, the size of the carpet sample, relative to the size of the canister, being such that the no portion of the sample touches another portion of the sample.
• the canisters are placed in the Launder-O-Meter and the water bath temperature is held at 110°F for 5 minutes.
• the temperature of the water bath is then raised to the desired temperature for application of the stain-resist composition.
• the temperature of the water bath is raised to 170°F ⁇ 5°F, and for application at pH 5, the temperature of the water bath is raised to 200°F ⁇ 5°F.
• the bath water reaches the desired temperature, it is held there for 20 min. and then cooled to 100°F.
• the treated carpet sample is removed from the canister and rinsed by squeezing in deionized water at room temperature. Three successive rinses in fresh deionized water are given, each rinse being at 40 volumes of water per volume of sample.
• the rinsed carpet sample is centrifuged to remove excess liquid and dried at 200°F. in a forced draft oven for 30 minutes. The dry carpet sample can then be tested by use of the tests described below.
• the Stain Test is used to measure the extent to which carpeting is stained by a commercial beverage composition which contains FD&C Red Dye No. 40 (an acid dye).
• the staining liquid if sold commercially as a liquid, is used as is.
• the commercial product is in the form of a solid.
• the beverage preparation in dry, solid form, is dissolved in deionized water so as to provide 0.1 g of FD&C Red Dye No. 40 per liter of water.
• Sufficient wetting agent Du Pont Merpol®SE liquid nonionic ethylene oxide condensate
• the test sample is DuPont type 1150 Nylon 6,6 (white); Superba heatset, mock dyed level loop carpet, 3/8 inch pile height, 30 ounces per yard, 1/10 inch gauge, 10 stitches per inch, woven polypropylene primary backing.
• test sample is wetted completely with water, and excess water is removed by centrifuging.
• the damp sample is placed tufted face down in a pan and covered with ten times its face weight of stain fluid. Entrained air is expelled from the sample by squeezing or pressing. The sample is turned over and again the air is expelled. The sample is then returned to a face down position, and the pan is covered for storage for desired test period, namely 30 minutes or 24 hours.
• the stored stain sample is rinsed in running cool water until no more stain is visually detectable in the rinse water.
• the rinsed sample is extracted in a centrifuge and dried at 200 degrees F.
• the Staining is evaluated with the Minolta Chroma Meter tristimulus color analyzer in the L*A*B Difference Mode with the target sample set for the unstained carpet.
• the "a" value is a measure of redness, with a value of 43 equal to that obtained on an untreated carpet.
• the light-fastness of carpet samples treated with a stainblocker is determined by exposing the treated samples to UV light for 20 Hours.
• a sample piece of carpet that has been treated with a stain-­blocker is placed in a box containing its hinged top a standard fluorescent fixture fitted with two forty watt lamps. Centered under the pair of lamps in the bottom of the box is a sliding tray having a 3 inch x 40 inch recess for holding carpet specimens. The depth of the recess is such that the distance from the carpet face to the plane defined by the lamp surfaces is 1 inch.
• the current to the lamp is controlled by a timer so that a twenty-hour exposure can be obtained automatically.
• the reflectance of CIE White Light Source C from the carpet is compared with the reflectance from an unexposed sample and the CIELAB delta “b” noted.
• Delta “b” is a measure of the yellow component of white light.
• a Minolta Chroma Meter model CR-110 reflectance meter is used to make the measurements and to calculate delta "b” automatically from stored data on the unexposed sample. The value of "b” is reported as the measure of yellowing with increasing positive values of "b” corresponding to increased degrees of yellowing.
• the Minolta Chroma Meter is used in the Hunter L*a*b color-deviation measuring mode [Richard Hunter, "Photoelectric Colorimetry with Three Filters,” J. Opt. Soc. Am., 32 , 509-538 (1942)].
• the instrument measures the color differences between a "target” color, whose tristimulus color values have been entered into the microprocessor as a reference, and the sample color presented to the measuring head of the instrument.
• the "target" color entered is that of the carpet before yellowing or staining.
• the color reflectance of the yellowed or stained carpet is then measured with the instrument and reported as: *E, the total color difference, *L, the lightness value, *a, the redness value, if positive, or greenness, if negative, and *b, the yellowness value, if positive, or blueness, if negative.
• the product solution thus obtained was applied to nylon carpet at 2-1/2 percent on weight of fiber in a simulated beck dyeing apparatus.
• the dried carpet was tested by saturating it with a solution of FD&C Red Dye No. 40 and letting it stand for 1/2 hour at room temperature (Stain Test described above). It was then rinsed with cold water.
• the treated carpet showed no evidence of staining while an untreated control was deeply stained red.
• the carpet was allowed to stand for 24 hours in the acid dye solution; on rinsing, the carpet treated with the above product showed a noticeable pink stain while the untreated carpet was again stained a deep red. When the 24 hr.
• SMAC 30 parts styrene/maleic anhydride copolymer (ARCO SMA®1000 resin), 36.2 parts water, 33.8 parts 30% NaOH combined and heated to hydrolyze the resin per the procedure described in Example 1.
• Na C12 SO4 30% aqueous sodium lauryl sulfate.
• PGME Propylene glycol monomethyl ether
• DPM Dipropylene glycol monomethyl ether
• Fluorosurfactant A mixture of Li fluoroalkyl mercapto propionate and diethanolammonium fluoroalkyl phosphate in a 1.0:1.1 ratio.
• SPFCAD in parts by weight, 29 parts of a sulfonated phenol-formaldehyde condensate (as described in Example 9 of said Liss et al. patent application), 44.5 parts of ethylene glycol, 21 parts of water, 4 parts of inorganic salts and 1.5 parts of acetic acid.
• the shampoo composition was diluted 19:1 with H2O and applied with a Tornado extraction carpet cleaner (3 passes) to T846, 2-ply, Superba heatset BCF Saxony carpet dyed to a light beige (representative of residential carpet). Visual inspection showed little or no yellowing.
• a blend were prepared from 20 parts by weight of the sulfonated phenol-formaldehyde condensate of Example 9 of the Liss and Beck application and 80 parts by weight of a hydrolized styrene/stilbene/maleic anhydride polymer, mol ratio of 0.75/0.25/1.0 (prepared substantially as described in EXAMPLE 7 of said Fitzgerald, Rao and Vinod patent application).
• the blend When tested for stain blocking in the aforesaid simulated Beck dying operation, the blend exhibited stain blocking properties.
• Two blends were prepared, each from 20 parts by weight of the condensate of Example 9 of the Liss and Beck application and 80 parts by weight of a hydrolized 4-hydroxystilbene/styrene/maleic anhydride terpolymer.
• the terpolymer mol ratio was 0.25/0.75/1.0, and in the other one, the mol ratio was 0.5/0.5/1.0 (prepared substantially as described in EXAMPLES 14 and 16 respectively of said Fitzgerald, Rao and Vinod patnt application).
• the blends When tested for stain blocking as described above, the blends exhibited stain blocking properties.

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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)
• Detergent Compositions (AREA)
• Carpets (AREA)

Priority Applications (1)

Applications Claiming Priority (8)

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Family Applications (1)

Country Status (8)

Cited By (16)

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Citations (3)

• 1988
  • 1988-12-14 DE DE88311826T patent/DE3880474T2/de not_active Expired - Lifetime
  • 1988-12-14 EP EP88311826A patent/EP0328822B1/fr not_active Expired - Lifetime
  • 1988-12-15 CA CA000586055A patent/CA1340028C/fr not_active Expired - Fee Related
  • 1988-12-20 NO NO88885656A patent/NO885656L/no unknown
  • 1988-12-20 FI FI885888A patent/FI885888A/fi not_active Application Discontinuation
  • 1988-12-20 KR KR1019880017196A patent/KR920006477B1/ko not_active IP Right Cessation
  • 1988-12-20 DK DK709988A patent/DK709988A/da not_active Application Discontinuation
  • 1988-12-21 JP JP63323213A patent/JPH0284570A/ja active Granted

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