EP0562024B1 - Fleckabweiser aus maleinsäureanhydrid/olefin-polymeren - Google Patents
Fleckabweiser aus maleinsäureanhydrid/olefin-polymeren Download PDFInfo
- Publication number
- EP0562024B1 EP0562024B1 EP92903258A EP92903258A EP0562024B1 EP 0562024 B1 EP0562024 B1 EP 0562024B1 EP 92903258 A EP92903258 A EP 92903258A EP 92903258 A EP92903258 A EP 92903258A EP 0562024 B1 EP0562024 B1 EP 0562024B1
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- Prior art keywords
- maleic anhydride
- alpha
- acid
- olefin
- polymer
- 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.)
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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
- D06M15/21—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
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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
- D06M15/21—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
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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
- 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
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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
- 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 a process for the synthesis of polyamide textile substrates treated with stain-resistant compositions comprising hydrolysed water-soluble maleic anhydride/ alpha-olefin polymers.
- 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 US-A-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 US-A-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 0329899, 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 (C4 ⁇ 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.
- the present invention provides a process for imparting stain resistance to a polyamide textile substrate wherein the substrate is treated with hydrolysed water-soluble maleic anhydride/alpha-olefin polymers.
- 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 alpha-olefin/maleic anhydride polymers of this invention, to be useful for this purpose was unexpected.
- the present invention relates to the use of hydrolysed water-soluble maleic anhydride/alpha-olefin polymers as stain-resists for fibrous polyamides.
- a variety of linear and branched chain alpha-olefins containing at least 4 carbon atoms can be used for the purposes of this invention.
- Particularly 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 C4 ⁇ 10, such as isobutylene, 1-butene, 1-hexene, 1-octene, and the like, with isobutylene being most preferred.
- alpha-olefins can be replaced by other monomers, e.g. up to 50 wt% of alkyl(C1 ⁇ 4) acrylates, alkyl(C1 ⁇ 4) methacrylates, vinyl acetate, vinyl chloride, vinylidine chloride, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixtures of the same.
- maleic anhydride A part (1-75%) of the maleic anhydride can be replaced by maleimide, N-alkyl(C1 ⁇ 4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C1 ⁇ 18) esters of the foregoing acids, cycloalkyl(C3 ⁇ 8) esters of the foregoing acids, sulfated castor oil, or the like.
- maleimide N-alkyl(C1 ⁇ 4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl(C1 ⁇ 18) esters of the foregoing acids, cycloalkyl(C3 ⁇ 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 interpolymers i.e. copolymers, terpolymers, and the like
- maleic anhydride and one or more 1-alkenes having at least 4 carbon atoms particularly isobutylene, 1-hexene and 1-octene
- polyamide substrates e.g. carpeting
- Copolymers of maleic anhydride with butadiene or 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 10 carbon atoms.
- 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 can be hydrolyzed to the free acid or their salts by reaction with water or alkali, or they can also be reacted with C1 ⁇ 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.
- stain-resists of the present invention can blend the stain-resists of the present invention with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in US-A-4,833,009 and US-A-4,965,325; methacrylic acid polymers disclosed in US-A-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 the stain-resists of the present invention with other known stain-resists, such as phenol-formaldehyde condensation products as disclosed in US-A-4,833,009 and US-A-4,965,325; methacrylic acid polymers disclosed in US-A-4,937,123; or hydrolized polymers of maleic anhydride and one or more ethylenically unsaturated aromatic compounds described by Fitzgerald
- the polymers suitable for the purposes of this invention contain between about 0.7 and 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 generally comprises between (a) 100 and 80 mol% of at least one 1-alkene containing 4 to 10 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, 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.
- 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. Generally, the maleic anhydride polymer should be sufficiently water-soluble that uniform application to a fiber surface can be achieved at an appropiate acidity.
- the olefin/maleic anhydride polymers of this invention can be used as such 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: padding, spraying, foaming in conjunction with foaming agents, batch exhaust in beck dyeing equipment, or continuous exhaust during a continuous dyeing operation. They can be applied by such methods to dyed or undyed polyamide textile substrates. In addition, they can be applied to such substrates in the absence or presence of a polyfluoroorganic oil-, water-, and/or soil- repellent materials. In the alternative, such a polyfluoroorganic material can be applied to the textile substrate before or after application of the polymers of this invention thereto.
- 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. 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 of this invention 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 polyfluoroorganic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described above, at temperatures described, and under acid conditions.
- 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 deg.C. The autoclave was then pressurized with propylene to 13.8 bar (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) (1mm Hg ⁇ 1,33 mbar) 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.
- the dye adsorbed onto the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of the Control.
- a number of 90 means 90% of the dye is adsorbed, indicating little stain resistance to the dye. The lower the number, the better is the resistance to stain.
- the results of the evaluation are set forth in TABLE 1.
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- 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)
Claims (9)
- Verfahren zur Verleihung von Fleckfestigkeit an ein textiles Polyamidsubstrat, welches umfaßt Auftragen auf das genannte Substrat einer wirksamen Menge einer Zusammensetzung, umfassend ein hydrolysiertes α-Olefin/Maleinsäureanhydrid-Polymer, das unter sauren Bedingungen wasserlöslich ist, worin das genannte Polymer zwischen 0,7 und 1,3 Polymereinheiten enthält, die sich von einem oder mehreren α-Olefin-Monomeren ableiten, die wenigstens 4 Kohlenstoffatome pro Polymereinheit, abgeleitet von Maleinsäureanhydrid, enthalten.
- Verfahren nach Anspruch 1, bei dem das genannte α-Olefin ein 1-Alken ist, das 4 bis 10 Kohlenstoffatome enthält.
- Verfahren nach Anspruch 1 oder 2, bei dem das α-Olefin ein terminal ungesättigtes Dien ist, das 4 bis 18 Kohlenstoffatome enthält.
- Verfahren nach einem der Ansprüche 1 bis 3, bei dem das Polymer bis zu 20 Mol-% eines 1-Alkens enthält, das 3 Kohlenstoffatome enthält.
- Verfahren nach einem der vorgenannten Ansprüche, bei das genannte Polymer etwa eine, sich von Maleinsäureanhydrid ableitende Polymereinheit pro Polymereinheit, die sich von einem oder mehreren α-Olefin-Monomeren ableitet, enthält.
- Verfahren nach einem der vorgenannten Ansprüche, bei dem wenigstens 95 Gew.-% der genannte Polymere ein Zahlenmittelmolekulargewicht von etwa 700 bis etwa 100 000 aufweisen.
- Verfahren nach einem der vorgenannten Ansprüche, bei dem bis zu 50 Gew.-% des genannten α-Olefins durch ein oder mehrere von C₁- bis C₄-Alkylacrylat oder Methacrylat, Vinylacetat, Vinylchlorid, Vinylidenchlorid, Vinylsulfid, N-Vinylpyrrolidon, Acrylnitril oder Acrylamid oder durch Gemische derselben ersetzt werden.
- Verfahren nach einem der vorgenannten Ansprüche, bei dem bis zu 75 Gew.-% des genannten Maleinsäureanhydrids durch Maleimid, N-Alkyl-(C₁-C₁₄)-maleimide, N-Phenylmaleimid, Fumarsäure, Itaconsäure, Citraconsäure, Aconitinsäure, Crotonsäure, Zimtsäure, Alkyl-(C₁₋₁₈)- oder Cycloalkyl-(C₃₋₈)-Ester der vorgenannten Säuren oder durch sulfatiertes Rizinusöl ersetzt werden.
- Verfahren nach Anspruch 1, bei dem bis zu 30 Gew.-% des Maleinsäureanhydrids durch Acryl- oder Methacrylsäure ersetzt werden.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94203127A EP0648886B1 (de) | 1990-12-13 | 1991-12-13 | Fleckabweiser aus Maleinanhydrid/Olefin-Polymeren |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US62688590A | 1990-12-13 | 1990-12-13 | |
US626885 | 1990-12-13 | ||
PCT/US1991/009155 WO1992010605A1 (en) | 1990-12-13 | 1991-12-13 | Maleic anhydride/olefin polymer stain-resists |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94203127A Division EP0648886B1 (de) | 1990-12-13 | 1991-12-13 | Fleckabweiser aus Maleinanhydrid/Olefin-Polymeren |
EP94203127.9 Division-Into | 1994-10-27 |
Publications (2)
Publication Number | Publication Date |
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EP0562024A1 EP0562024A1 (de) | 1993-09-29 |
EP0562024B1 true EP0562024B1 (de) | 1995-05-10 |
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP94203127A Expired - Lifetime EP0648886B1 (de) | 1990-12-13 | 1991-12-13 | Fleckabweiser aus Maleinanhydrid/Olefin-Polymeren |
EP92903258A Expired - Lifetime EP0562024B1 (de) | 1990-12-13 | 1991-12-13 | Fleckabweiser aus maleinsäureanhydrid/olefin-polymeren |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP94203127A Expired - Lifetime EP0648886B1 (de) | 1990-12-13 | 1991-12-13 | Fleckabweiser aus Maleinanhydrid/Olefin-Polymeren |
Country Status (9)
Country | Link |
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EP (2) | EP0648886B1 (de) |
JP (1) | JPH06503386A (de) |
AU (1) | AU660639B2 (de) |
CA (1) | CA2098120A1 (de) |
DE (2) | DE69132592T2 (de) |
IE (1) | IE914340A1 (de) |
MX (1) | MX9102558A (de) |
WO (1) | WO1992010605A1 (de) |
ZA (1) | ZA919847B (de) |
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 (de) | 1998-03-24 | 2001-01-17 | Avantgarb LLC | Modifizierte textilien und andere materialien sowie verfahren zu deren herstellung |
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/de not_active Expired - Lifetime
- 1991-12-13 CA CA002098120A patent/CA2098120A1/en not_active Abandoned
- 1991-12-13 EP EP92903258A patent/EP0562024B1/de 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 (de) | 1993-09-29 |
ZA919847B (en) | 1993-06-14 |
EP0648886B1 (de) | 2001-04-25 |
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 (de) | 1995-04-19 |
JPH06503386A (ja) | 1994-04-14 |
MX9102558A (es) | 1992-06-01 |
EP0648886A3 (de) | 1996-05-15 |
WO1992010605A1 (en) | 1992-06-25 |
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