EP0648886B1 - Maleic anhydride/olefin polymer stain resists - Google Patents
Maleic anhydride/olefin polymer stain resists Download PDFInfo
- Publication number
- EP0648886B1 EP0648886B1 EP94203127A EP94203127A EP0648886B1 EP 0648886 B1 EP0648886 B1 EP 0648886B1 EP 94203127 A EP94203127 A EP 94203127A EP 94203127 A EP94203127 A EP 94203127A EP 0648886 B1 EP0648886 B1 EP 0648886B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- maleic anhydride
- acid
- polymer
- alpha
- substrate
- 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.)
- Expired - Lifetime
Links
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
- D06M15/21—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
- D06M15/21—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
-
- 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
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
-
- 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
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- 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
- D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
-
- 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
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
-
- 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
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
-
- 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
- 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
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/11—Oleophobic properties
-
- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Definitions
- the present invention relates to polyamide textile substrates treated with stain-resistant compositions comprising water-soluble or water-dispersible maleic anhydride/ alpha-olefin polymers, and processes for their synthesis.
- the substrates of this invention possess stain-resistance but do not suffer from yellowing to the extent that some previously known materials do.
- Polyamide substrates such as nylon 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 et al. in U.S. Patent No. 4,963,409, disclose stain-resistant synthetic polyamide textile substrates having deposited on them sulfonated phenol-formaldehyde polymeric condensation products.
- sulfonated phenol-formaldehyde condenation products are themselves subject to discoloration; commonly they turn yellow.
- Yellowing problems are described by W. H. Hemmpel in a March 19, 1982 article in America's Textiles , entitled Reversible Yellowing Not Finisher's Fault. Hemmpel attributes yellowing to exposure of a phenol-based finish to nitrogen oxides and/or ultraviolet radiation. To deal with the yellowing problem, the condensation products were modified by Liss et al.
- the modified condensation products were dissolved in a hydroxy-containing solvent, such as ethylene glycol prior to there being applied to the textile substrate.
- 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 styrenemaleic 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.
- Fitzgerald et al. in EP-A 0 329 899, disclose the usefulness of aqueous solutions of hydrolyzed vinylaromatic/maleic anhydride copolymers in the treatment of textiles to render them resistant to staining.
- the preferred copolymer of Fitzgerald et al. is a hydrolyzed styrene/maleic anhydride copolymer.
- Fitzgerald et al. disclose that the monoalkyl ester of their maleic anhydride/vinyl aromatic polymer was ineffective as a stain-resist.
- maleic anhydride/alpha-olefin polymers are known.
- EP-A 306,992 published 15 March 1989 discloses maleic anhydride/-1-alkene (C 4-30 ) polymers.
- Florjanczyk et al. in Terpolymerization of Maleic Anhydride With Vinyl Monomers, J. Polymer SCI., Part A: Polym. Chem., 27 (12), 4099-108 disclose terpolymers of maleic anhydride with (i) 1-hexene, propylene, isobutylene, styrene, isoprene or 1,3-butadiene, and (ii) methyl methacrylate, methyl acrylate or acrylonitrile.
- EP-A-0 177 972 discloses an aqueous fabric finishing composition containing a solubilised copolymer of a 1-alkene having at least 10 carbon atoms and maleic anhydride.
- EP-A-0 332 342 discloses imparting stain resistance to fibrous polyamide using aqueous compositions of copolymers of methacylic acid with a monocarboxylic acid or a mono olefin.
- the present invention is based on the finding that polyamide fibrous substrates treated with specified water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers have stain-resistance.
- prior art materials known to be useful as stain-blockers were sulfonated phenol-formaldehyde condensates (excepting those of Fitzgerald et al, supra).
- Finding a non-sulfonated material, such as the water-soluble or water-dispersible alpha-olefin/maleic anhydride polymers of this invention, to be useful for this purpose was unexpected.
- the present invention provides a polyamide fibrous substrate having deposited on it an amount of a composition effective to impart stain-resistance to said substrate comprising a water-soluble or water-dispersible alphaolefin/maleic anhydride polymer or a mixture of said polymers, wherein said polymer contains from 0.7 to 1.3 polymer units derived from one or more alpha-olefin monomers per polymer unit derived from maleic anhydride and has been hydrolysed to the corresponding free acid or salt thereof or converted to a C 1-4 alkyl monoester, the alpha-olefin content of said polymer comprising between (a) 100 and 80 mol percent of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated diene containing 4 to 18 carbon atoms and (b) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms.
- the present invention relates to the use of certain water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers, or mixtures of the same, as stain-resists for fibrous polyamides.
- a variety of linear and branched chain alpha-olefins can be used for the purposes of this invention.
- Useful alpha-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-1,5-hexadiene; 1-alkenes containing 4 to 8 carbon atoms, such as isobutylene, 1-butene, 1-hexene, 1-octene, with isobutylene being most preferred.
- a part of the alpha-olefins can be replaced by other monomers, e.g. up to 50 wt% of vinyl acetate, vinyl chloride, vinylidine chloride, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixtures of the same.
- a part (1-75%) of the maleic anhydride can be replaced by maleimide, N-alkyl(C 1-4 ) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C 1-18 ) esters of the foregoing acids, cycloalkyl(C 3-8 ) esters of the foregoing acids, sulfated castor oil, or the like.
- At least 95 wt% of the maleic anhydride co- or terpolymers have a number average molecular weight of in the range between about 700 and 200,000, preferrably between about 1000 and 100,000.
- water-soluble or water-dispersible interpolymers i.e. copolymers, terpolymers, and the like
- maleic anhydride and one or more 1-alkenes having 4 to 8 carbon atoms particularly isobutylene, 1-hexene and 1-octene
- polyamide substrates e.g. carpeting
- Copolymers of maleic anhydride with propylene were found by the inventor to be less effective as stain-resists on such substrates than were interpolymers of maleic anhydride and 1-alkenes containing 4 to 8 carbon atoms.
- copolymers of maleic anhydride and at least one olefin selected from ethylene and 1-alkenes having 10 to 24 carbon atoms impart no detectable stain-resistance to such substrates.
- the maleic anhydride polymers useful in the present invention can be prepared according to methods well-known in the art.
- the maleic anhydride polymers thus obtained are hydrolyzed to the free acid or their salts by reaction with water or alkali, or they are reacted with C 1-4 alkyl alcohol to provide polymeric alpha-olefin/maleic acid monoesters, which have stainblocking properties.
- the hydrolyzed maleic anhydride polymer, or the monoester polymer should be sufficiently water-soluble that uniform application to a fibrous polyamide surface can be achieved at an appropriate acidity.
- applications using water dispersions of the polymer mixed with a suitable surfactant may be used to impart stain-resistance.
- stain-resists of the present invention can blend with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in U.S. Patents 4,833,009 and 4,965,325; methacrylic acid polymers disclosed in U.S. Patent No. 4,937,123; or hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald et al., supra.
- stain-resists of the present invention can blend with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in U.S. Patents 4,833,009 and 4,965,325; methacrylic acid polymers disclosed in U.S. Patent No. 4,937,123; or hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald et al., supra.
- the polymers suitable for the purposes of this invention contain between from 0.7 to 1.3 polymer units derived from one or more alpha-olefin monomers per polymer unit derived from maleic anhydride.
- the alpha-olefin content of the polymers of this invention comprise between (a) 100 and 80 mol% of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated diene containing 4 to 18 carbon atoms and (b) 0 to 20 mol% of at least one 1-alkene containing 3, or 10 to 18, carbon atoms.
- Polymers containing about one polymer unit derived from one or more olefin monomers per polymer unit derived from maleic anhydride are most effective in imparting stain resistance to textile substrates.
- the molecular weight of the polymers useful in the invention does not appear to be a limitation so long as the polymers are water-soluble or water-dispersible.
- hydrolyzed isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 impart good stain-resistance to polyamide substrates.
- water-soluble isobutylene/maleic anhydride copolymers having number average molecular weights between about 6000 and 100,000 remained in solution in water at 60°C.
- the polymers suitable for the purposes of this invention can be prepared by hydrolyzing the maleic anhydride/olefin polymers according to methods well-known in the art. For example, they can be hydrolyzed to the free acid or their salts by reaction with water or alkali.
- the maleic anhydride polymer should be sufficiently water-soluble that uniform application to a fiber surface can be achieved at an appropiate acidity.
- applications using dispersions of the polymers with suitable surfactants may be used to impart stain-resistance.
- olefin/maleic anhydride polymers disclosed herein are used in treating polyamide textile substrates. They can be effectively applied to polyamide fibrous substrates by a wide variety of methods known to those skilled in the art, such as:
- the quantities of the polymers disclosed herein which are applied to the textile substrate are amounts effective in imparting stain-resistance to the substrate. Those amounts can be varied widely; in general, one can use between 1 and 5% by weight of them based on the weight of the textile substrate, usually 2.5% by weight or less.
- the polymers can be applied, as is common in the art, at pHs ranging between about 2 and 7. However, more effective exhaust deposition can be obtained at a pH as low as 1.5. When the latter low pH is used, the preferred level of application to the textile substrate is about 2.5% by weight, based on the weight of the textile substrate. In an embodiment, a pH between about 2 and 3 is used.
- stainblocking is obtained if the polymers are applied to the textile substrate at either 20°C followed by heat treatment at a temperature in the range between about 50 and 150°C for about 1 to 60 minutes, or applied at temperatures in the range between about 40 and 95°C for about 1 to 60 minutes. For example, at a pH between about 2 and 3, a temperature between about 70 and 90°C is preferred. However, stain-blocking can be obtained when application is effected even at that of cold tap water (10-15°C).
- the polymers disclosed herein can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation or in the form of aqueous shampoo preparation, with or without one or more polyfluoro-organic 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.
- a 500 ml autoclave was charged with 40 g of maleic anhydride (0.408 mole), 300 ml of ethylbenzene and 4.3 g of 70 wt% of benzoyl peroxide. It was closed, vented twice with propylene and heated under stirring to 70 °C. The autoclave was then pressurized with propylene to 1379 kPa (200 psi). After agitation for 3 hours at 70°C, a solution of 2.7 g of 70 wt% benzoyl peroxide in 10 ml of ethylbenzene was blown into the reactor and the reaction was continued at 70°C for another 14 hours. The vessel was then cooled and vented.
- the maleic anhydride/propylene copolymer product in form of a dispersion, was discharged and filtered giving 46.7 g of a white powder having a number average molecular weight, by gel permeation chromatography (GPC), of 2150.
- GPC gel permeation chromatography
- a portion of the solid copolymer (10 g) was hydrolyzed at 80-95°C in the presence of 82.5 g deionized water, 6.7 g 30 wt% sodium hydroxide and 2 drops of a 1% solution of benzyltriethylammonium chloride resulting after about 1 to 2 hours in a clear solution containing 10 wt% of a water-soluble maleic anhydride/propylene copolymer.
- An isobutylene/maleic anhydride copolymer (50 parts) having a number average molecular weight (GPC) of 32,000, commercially available from Kuraray Co. (Japan) as "Isobam”-04, was reacted under agitation with methanol (50 parts) at reflux temperature (about 65°C) for 23 hours. Excess methanol was then removed at reduced pressure (20 mm Hg) at 70-90°C to give the isobutylene/maleic acid monomethyl ester which was then dissolved at room temperature in dilute ammonium hydroxide ( 2.5 parts of ammonia in 356 parts of water) to give a 14.5 wt % solution.
- GPC number average molecular weight
- Nylon fiber was treated with 1.2 wt% or 2.4 wt% stain resist at a goods-to-liquor ratio of 1:32 at a pH of 2.0 or 2.35 for 45 minutes at 80 or 95°C.
- the fiber was then washed, air-dried and exposed at room temperature to a dye solution consisting of 0.2 g of FD&C Red Dye No. 40 and 3.2 g of citric acid in 1 liter of deionized water at a goods-to-liquor ratio of 1:40. After approximately 65 hours, the dye adsorbed onto the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of the Control.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US62688590A | 1990-12-13 | 1990-12-13 | |
US626885 | 1990-12-13 | ||
EP92903258A EP0562024B1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain-resists |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92903258A Division EP0562024B1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain-resists |
EP92903258.9 Division | 1991-12-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0648886A2 EP0648886A2 (en) | 1995-04-19 |
EP0648886A3 EP0648886A3 (en) | 1996-05-15 |
EP0648886B1 true EP0648886B1 (en) | 2001-04-25 |
Family
ID=24512269
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94203127A Expired - Lifetime EP0648886B1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain resists |
EP92903258A Expired - Lifetime EP0562024B1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain-resists |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92903258A Expired - Lifetime EP0562024B1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain-resists |
Country Status (9)
Country | Link |
---|---|
EP (2) | EP0648886B1 (es) |
JP (1) | JPH06503386A (es) |
AU (1) | AU660639B2 (es) |
CA (1) | CA2098120A1 (es) |
DE (2) | DE69132592T2 (es) |
IE (1) | IE914340A1 (es) |
MX (1) | MX9102558A (es) |
WO (1) | WO1992010605A1 (es) |
ZA (1) | ZA919847B (es) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX9301644A (es) * | 1992-03-25 | 1993-09-01 | Du Pont | Substrato fibroso de poliamida, composicion y proceso para impartir resistencia a la decoloracion a tal substrato. |
WO1994018376A1 (en) * | 1993-02-02 | 1994-08-18 | E.I. Du Pont De Nemours And Company | Durable hydrolized maleic anhydride polymer stain-resists |
US5520962A (en) * | 1995-02-13 | 1996-05-28 | Shaw Industries, Inc. | Method and composition for increasing repellency on carpet and carpet yarn |
US5770656A (en) * | 1995-09-22 | 1998-06-23 | E.I. Du Pont De Nemours And Company | Partial fluoroesters or thioesters of maleic acid polymers and their use as soil and stain resists |
DE69724765T2 (de) * | 1996-02-23 | 2004-07-15 | E.I. Du Pont De Nemours And Co., Wilmington | Schmutzabweisende mischungen aus polymeren mit carboxylgruppen und resol-harzen |
US6197378B1 (en) | 1997-05-05 | 2001-03-06 | 3M Innovative Properties Company | Treatment of fibrous substrates to impart repellency, stain resistance, and soil resistance |
EP1068387A2 (en) | 1998-03-24 | 2001-01-17 | Avantgarb LLC | Modified textile and other materials and methods for their preparation |
US6380336B1 (en) | 1998-03-24 | 2002-04-30 | Nano-Tex, Llc | Copolymers and oil-and water-repellent compositions containing them |
US6068805A (en) * | 1999-01-11 | 2000-05-30 | 3M Innovative Properties Company | Method for making a fiber containing a fluorochemical polymer melt additive and having a low melting, high solids spin finish |
US6207088B1 (en) | 1999-01-11 | 2001-03-27 | 3M Innovative Properties Company | Process of drawing fibers through the use of a spin finish composition having a hydrocarbon sufactant, a repellent fluorochemical, and a fluorochemical compatibilizer |
US6117353A (en) * | 1999-01-11 | 2000-09-12 | 3M Innovative Properties Company | High solids spin finish composition comprising a hydrocarbon surfactant and a fluorochemical emulsion |
US6120695A (en) * | 1999-01-11 | 2000-09-19 | 3M Innovative Properties Company | High solids, shelf-stable spin finish composition |
US6537662B1 (en) | 1999-01-11 | 2003-03-25 | 3M Innovative Properties Company | Soil-resistant spin finish compositions |
US6077468A (en) | 1999-01-11 | 2000-06-20 | 3M Innovative Properties Company | Process of drawing fibers |
CN100506927C (zh) | 2005-03-21 | 2009-07-01 | 刘景春 | 多质离散效应纳米结构液膜及其制备方法和应用 |
US7579420B2 (en) | 2006-04-04 | 2009-08-25 | E. I. Du Pont De Nemours And Company | Hyperbranched maleic anhydride-diene polymers |
US7579403B2 (en) | 2006-04-04 | 2009-08-25 | E. I. Du Pont De Nemours And Company | Stain resist comprising hyperbranched maleic anhydride-diene polymers |
US7914890B2 (en) | 2007-12-19 | 2011-03-29 | E.I. Dupont De Nemours And Company | Cyclic olefin-maleic acid copolymers for stain resists |
CN105829516A (zh) | 2013-11-11 | 2016-08-03 | 艺康美国股份有限公司 | 具有强化的污垢控制和污物分散的高碱性餐具清洗洗涤剂 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4623683A (en) * | 1984-10-12 | 1986-11-18 | S.C. Johnson & Son, Inc. | Fabric finish with alpha olefin resins and process |
US4871823A (en) * | 1987-09-11 | 1989-10-03 | S. C. Johnson & Son, Inc. | 1-Alkene/excess maleic anhydride polymers |
KR920006476B1 (ko) * | 1987-12-21 | 1992-08-07 | 이 아이 듀우판 디 네모아 앤드 캄파니 | 방오성 폴리아미드 직물 지지체 및 직물 지지체에 방오성을 제공하는 방법 |
AU627711B2 (en) * | 1988-03-11 | 1992-09-03 | Minnesota Mining And Manufacturing Company | Process for providing polyamide materials with stain resistance |
-
1991
- 1991-12-13 ZA ZA919847A patent/ZA919847B/xx unknown
- 1991-12-13 WO PCT/US1991/009155 patent/WO1992010605A1/en active IP Right Grant
- 1991-12-13 DE DE69132592T patent/DE69132592T2/de not_active Expired - Lifetime
- 1991-12-13 DE DE69109694T patent/DE69109694T2/de not_active Expired - Lifetime
- 1991-12-13 IE IE434091A patent/IE914340A1/en not_active Application Discontinuation
- 1991-12-13 JP JP4503687A patent/JPH06503386A/ja active Pending
- 1991-12-13 EP EP94203127A patent/EP0648886B1/en not_active Expired - Lifetime
- 1991-12-13 CA CA002098120A patent/CA2098120A1/en not_active Abandoned
- 1991-12-13 EP EP92903258A patent/EP0562024B1/en not_active Expired - Lifetime
- 1991-12-13 MX MX9102558A patent/MX9102558A/es unknown
- 1991-12-13 AU AU91573/91A patent/AU660639B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE69109694D1 (de) | 1995-06-14 |
IE914340A1 (en) | 1992-06-17 |
EP0562024A1 (en) | 1993-09-29 |
ZA919847B (en) | 1993-06-14 |
AU9157391A (en) | 1992-07-08 |
AU660639B2 (en) | 1995-07-06 |
CA2098120A1 (en) | 1992-06-14 |
DE69132592D1 (de) | 2001-05-31 |
DE69109694T2 (de) | 1996-01-11 |
DE69132592T2 (de) | 2001-10-18 |
EP0648886A2 (en) | 1995-04-19 |
JPH06503386A (ja) | 1994-04-14 |
MX9102558A (es) | 1992-06-01 |
EP0648886A3 (en) | 1996-05-15 |
EP0562024B1 (en) | 1995-05-10 |
WO1992010605A1 (en) | 1992-06-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0648886B1 (en) | Maleic anhydride/olefin polymer stain resists | |
US5707708A (en) | Maleic anhydride/olefin polymer stain-resists | |
US5460887A (en) | Stain-resistant polyamide substrates | |
EP0564591B1 (en) | Maleic anhydride/vinyl or allyl ether polymer stain-resists | |
US5654068A (en) | Stain resists for polyamide substrates | |
US6074436A (en) | Carpet treatment composition comprising polycarboxylate salts | |
US5708087A (en) | Carboxylic acid-containing polymer/resole stain-resists | |
EP0632856B1 (en) | Stain-resists for polyamide substrates | |
US5945493A (en) | Fluorine-containing maleic acid terpolymer soil and stain resists | |
US5744201A (en) | Method for treating carpet using PH adjustment | |
CA2231439C (en) | Treatment of polyamide materials with partial fluoroesters or fluorothioesters of maleic acid polymers and sulfonated aromatic condensates | |
EP1730346B1 (en) | Stain-resist compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 562024 Country of ref document: EP |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB |
|
17P | Request for examination filed |
Effective date: 19951019 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB |
|
17Q | First examination report despatched |
Effective date: 19980805 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AC | Divisional application: reference to earlier application |
Ref document number: 562024 Country of ref document: EP |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB |
|
REF | Corresponds to: |
Ref document number: 69132592 Country of ref document: DE Date of ref document: 20010531 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20101224 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20101117 Year of fee payment: 20 Ref country code: GB Payment date: 20101208 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20101208 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69132592 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69132592 Country of ref document: DE |
|
BE20 | Be: patent expired |
Owner name: E.I. *DU PONT DE NEMOURS AND CY Effective date: 20111213 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20111212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111212 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20111214 |