AU664268B2 - Stain-resists for polyamide substrates - Google Patents

Description

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OPI DATE 21/10/93 AOJP DATE 23/12/93 APPLN. ID 39353/93 PCT NUMBER PCT/US93/02805 AU9339353

(PCT)

I IN I MIXiINt-xI £J ,I L (51) International Patent Classification 5 (11) International Publication Number: WO 93/19238 DO6M 15/41, 15/263, 15/21 A l (43) International Publication Date: 30 September 1993 (30.09.93) (21) International Application Number: PCT/US93/02805 (81) Designated States: AU, CA. Fl, JP. KR, NO. European patent (AT. BE, CH, DE. DK, ES, FR. GB. GR, IE, IT.

(22) International Filing Date: 25 March 1993 (25.03.93) LU, MC, NL, PT, SE).

Priority data: Published 07/857,178 25 March 1992 (25.03.92) US With international search report.

07/857,179 25 March 1992 (25,03.92) US Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

(71) Applicant: E.I. DU PONT DE NEMOURS AND COM- PANY [US/US]; 1007 Market Street, Wilmington, DE 19898 (US).

(72) Inventor: PECHHOLD, Engelbert 12 Harvey Lane, Chadds Ford, PA 19317 (US).

(74)Agents: FEENY, Charles, E. et al.; E.I. du Pont de Nemours and Company, Legal/Patent Records Center, 1007 Market Street, Wilmington, DE 19898 (US).

(54)Title: STAIN-RESISTS FOR POLYAMIDE SUBSTRATES (57) Abstract A stain-resist for polyamide textiles comprises blends of maleic anhydride/alpha-olefin polymers with sulfonated phenolformaldehyde condensation products. The stain-resist blends are water-soluble at low pH, even in the absence of surfactant, and are strongly substantive and more resistant to yellowing than the condensation products.

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r 7 ^~lri pr1 WO 93/19238 PCT/US93/02805 Title Stain-Resists for Polyamide Substrates Cross Reference to Related Applications This application is a continuation-in-at- U.Application Serial Number 07/809,843 filed Dece b which in turn is a continuation-in-part of U.S. on erial Number 07/626,885 filed December 13, 1990.

Field of the Invention The present invention relates to polymeric stain-resist compositions.

Background of the Invention Polyamide substrates, such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, 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 composition containing a sulfonated phenol-formaldehyde condensation product to the substrate. However, sulfonated phenolformaldehyde condensation products are themselves subject to discoloration; commonly they turn yellow. Yellowing problems are described by W.

H. Hemmpel in a March 19, 1932 article in America's Textiles, entitled "Reversible Yellowing Not Finisher's Fault". Hemmpel attributes yellowing to exposure of a 2 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. in U.S. Patent Number 4,963,409 by acylation or etherification of some of the phenolic hydroxyls. My U.S. Application Serial Number 07/809,843 filed December 18, 1991, of which this is a continuation-in-part, deslseand claims polyamide fibrous substrates treated with water-soluble or water-dispersible maleic anhydride/alpha-olefin polymers to make them stain resistant and methods for preparing them. Stain-resistant polyamide substrates treated with the compositions of this invention are disclosed and claimed in my copending application filed of even date herewith, Attorney Docket No. CH-2261.

Brief Summary of the Invention The present invention provides a composition useful for imparting stain resistance to a polyamide fibrous substrate comprising a water-soluble or water-dispersible alpha-olefin/maleic anhydride polymer or a mixture of said polymers and I- 2 (ii) a sulfonated phenol-formaldehyde condensation product, which is useful as a dye resist agent, a dye fixing agent, a dye reserving agent or an agent which improves the wet-fastness of dyeing on polyamide fibers.

The compositions of the present invention show enhanced durability, to shampoo washing of polyamide substrates treated with the compositions. In addition, the invention provides stain resists which are more resistant to yellowing when exposed to UV light or NOx gases than are the sulfonated phenol/formaldehyde condensates. At least some embodiments of the invention seek to provide a stain-resistant composition capable of imparting good stain resistance together with a low propensity to yellowing and having good substantive properties. A further problem associated with prior art compositions is that they have low solubility in water at the low pH preferably S used to treat textile articles unless surfactant is used. At least some embodiments of the invention seek to provide a stain-resistant composition having a good water-solubility.

According to the presant invention there is provided a composition useful for imparting stain resistance to a polyamide fibrous substrate comprising: a water-soluble or water-dispersible alpha-olefin/maleic anhydride polymer or a mixture of said polymers wherein said polymer contains 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 said polymer comprising between 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 (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms, and a sulfonated phenol-formaldehyde condensation product, the weight ration of A:B being in the range between about 5:95 and 95:5.

According to a further embodiment of the present invention there is provided a polyamide fibrous substrate having deposited on it an amount of a composition effective to impart stain-resistance to said substrate comprising: S(A) a water-soluble or water-dispersible alpha-olefin/maleic anhydride V 59/95MSAP7844.SPE,2 Ey 14 i r V 2a polymer or a mixture of said polymers wherein said polymer contains 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 said polymer comprising between 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 (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms, and a sulfonated phenol-formaldehyde condensation product, the weight ratio of A:B being in the range between about 5:95 and 95:5.

According to still another embodiment of the present invention there is provided a process for imparting stain-resistance to a polyamide textile substrate which comprises applying to said substrate together or separately in S amounts effective to impart stain-resistance to said substrate: a water-soluble or water-dispersible alpha-olefin/maleic anhydride polymer or a mixture of said polymers wherein said polymer contains between about 0.7 and 1.3 polymer units derived from one or more alphaolefin monomers per polymer unit derived from maleic anhydride. The alphaolefin content of said polymer comprising between 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 (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms, and a sulfonated phenol-formaldehyde condensation product, the ta weight ratio of A:B being in the range between about 5:95 and 95:5.

Detailed Description of the Invention The Blend The two components may be blended together in a wide range of relative proportions. For example, the weight ratio of maleic anhydride copolymer to resin may lie in the range of between about 95:5 and 5:95, preferably between about 90:10 and about 10:90, more preferably between about 60:40 40:60.

The pH of the blend is adjusted to the required pH preferably in the range about 1 to 3 more preferably 1.5 to 2.5 with acid. Surprisingly the stain-resistant 5/9/95MSAP7844.SPE,2 -I I F, "'WT I 1 to 3 more preferably 1.5 to 2.5 with acid. Surprisingly the stain-resistant composition of the present invention remains clear at such low pH. This finding is advantageous since the stain-resistant composition of this invention need not contain any surfactant to solubilize the active ingredient. If desired however, the composition may contain a surfactant. Higher pH in the range up to about pH 7 to 9 may be used as well.

The maleic anhydride/alpha-olefin polymer The polymers useful for the purposes of this invention comprise one or more water-soluble or water-dispersible hydrolyzed maleic anhydride polymers.

A variety of linear and branched chain alpha-olefins can be used for the purposes of this invention. Particularly useful alpha-olefins are dienes containing 4 to 8 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, and the like, with isobutylene being 1 5 most preferred. A part of the alpha-olefins can be replaced by other S monomers, up t t t (r t t 5/9/95MSAP7844.SPE,2 i WO 93/19238 PCT/US93/02805 3 to 50 wt% of alkyl (C 1 4 acrylates, alkyl (C 1 4 methacrylates, vinyl sulfides, Nvinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixture of the same.

A part (preferably 1-75% by weight) 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- 1 8 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, preferably between about 1,000 and 100,000.

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 aqueous 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 polymers suitable for the purposes of this invention contain between about 0.7 and 1.3 polymer units derived from one ore more alpha-olefin monomers per polymer unit derived from maleic anhydride. The alpha-olefin content of the polymers of this invention comprise between 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 0 to 20 mol% of at least one 1alkene 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 waterdispersible. Thus, for example, hydrolyzed isobutylene/maleic anhydride copolymer having number average molecular weights between about 6,000 and 100,000 impart good stain-resistance to polyamide substrates. Even at a pH as low 3 o as 1.5, water-soluble isobutylene/maleic anhydride copolymers having number average molecular weights between about 6,000 and 100,000 remained in solution in water at 60 0

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.

r Ii WO 93/19238 PCT/US93/02805 Suitable maleic anhydride polymers can conveniently obtained by hydrolysis of "Isobam"-01, an isobutylene maleic anhydride copolymer of molecular weight around 10,000, "Isobam"-04 a similar polymer having a molecular weight of around 40,000 or "Isobam"-10 a similar polymer having a molecular weight of around 100,000 with sodium hydroxide. Other suitable maleic anhydride polymers include BM-30 available from Kuraray Co. (Japan). BM-30 is an isobutylene/maleic anhydride/N-phenylmaleimide terpolymer having a molecular weight of around 40,000. A commercially available product usable without further treating is "Lindron" 10 (ex Lindau Chemical), a butadiene/maleic anhydride copolymer having a molecular weight of about 5,000 to 10,000. Other suitable copolymers include monoesters of C 4 8 alpha-olefin/maleic anhydride copolymers.

The monoesters can be obtained by a range of reactions well known to those skilled in the art. A preferred method is by reaction with an alcohol by heating under reflux with the alcohol and then removing excess alcohol. Preferred alcohols are C1- 6 alcohols especially methanol and ethanol.

Preparation of maleic anhydride/alpha-olefin polymers is also described in U.S. Reissue Patent No. 28,475, in EP 306992 and by Florjanczyk et al.

in J. Polymer SCI., Part A, Polymer Chem., 27 (12) pages 4099 to 4108, the disclosure of which is specifically incorporated by reference. These references 2 0 contain further teaching of techniques for the preparation of such polymers.

The sulfonated phenol-formaldehyde resin The sulfonated phenol-formaldehyde condensation products which can be used for the purposes of this invention include any sulfonated hydroxy aromatic-formaldehyde condensation products which have been 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 or dyeings on polyamide fibers. See for example U.S. 4,592,940, U.S. 4,591,591, U.S. 3,790,344 and GB 1,291,784, the disclosure of which is specifically incorporated herein by reference.

Examples of commercially available condensation products suitable for the invention are MESITOL NBS, product of Bayer AG (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, a product of Ciba-Geigy SCorp., (formed by condensing a mixture of naphthalene monosulfonic acid, bis(hydroxyphenyl) sulfone and formaldehyde; U.S. Patent Number 3,716,393) and "Erional" LY. The sulfonated hydroxyaromatic formaldehyde products sold as WO 93/19238 PC/US93/02805 "Stainfree" by Cybron Chemicals and "Algard" NS by Allied Colloid Co. are also suitable.

Application The stain-resistant composition 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. The stain-resist components of the presert invention can be applied to the substrate separately or together as a blend. In the case of the present invention, stainresistance of polyamide substrates is slightly better if the maleic anhydride/olefin polymer is applied to the polyamide substrate followed by the sulfonated phenol/formaldehyde condensate. On the other hand, carpet mills in general prefer to apply components of a stain-resist mixture together, and such would be expected with the composition of this invention.

The stain resistant compositions of this invention can be applied by the foregoing 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 compositions of this invention thereto.

More effective stainblocking is obtained if the stain-resistant compositions are applied to the textile substrate at either 20 0 C followed by heat treatment at a temperature in the range between about 50 to 150 0 C for about 1 to 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 0 C is preferred. However, stain-blocking can be obtained when application is effected even at that of cold tap water (10-15 0

C).

The stain-resistant compositions of this invention can also be applied in situ 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 I-I ~1 ja-- WO 93/19238 PCT/US93/02805 6 levels described above, at temperature described, and at a pH between about 1 and 9, preferably between about 2 and 7.

In the Examples that follow, all viscosities were determined at room temperature about 20°C and all percentages are by weight, and the following application and testing procedures were used.

Method of Application A light blue dyed cut-pile carpet constructed from 70 oz/sqy.d_.

superba-set BCF nylon 66 is treated in a laboratory Beck apparatus for 20 minutes at 80°C (176°F) at a 20:1 liquor-to-goods ratio with a solution of a stain resist agent described in one of the examples of pH of 2.0 and in the presence of 2.0 g per liter of magnesium sulfate to give an application load of 0.8% owf. Based on active ingredients. The carpet was then rinsed under tap water, partially de-watered by squeezing and dried in an forced-air oven for about 20 minutes at 121°C (250°F). A commercially available latex composition (Textile Rubber Co. Calhoun, GA) was applied as to carpet backing adhesive, with a secondary polypropylene backing under the trade name Actionbac (AMOCO, Atlanta, GA).

Stain Test A carpet specimen (3x5 inch) was placed on a flat non-absorbent surface. 20 ml of a solution made from 45 g of cherry-flavored, sugar sweetened, commercially available dilutable soft drink containing FD&C Red Dye No. 40 and 500 ml of water was poured into a 2linch diameter cylinder which was tightly placed over the specimen. The cylinder was removed after all the liquid had been i absorbed. The stained carpet specimen was left undisturbed for 24 hours, after which it was rinsed thoroughly under cold tap water and squeezed dry. The 2 5 specimens were visually inspected and the amount of color remaining in the stained area rated according to the following stain rating scale: no staining 4 slight staining 3 noticeable staining 2 considerable staining 1 heavy staining In other words, a stain rating of 5 is excellent, showing outstanding stain resistance, whereas 1 is the worst rating comparable to an untreated control sample.

L i 1 WO 93/19238 PCT/US93/02805 7 Shampoo Wash Durability Test A 3x5 inch carpet specimen was submerged for 5 minutes at room temperature in a detergent solution consisting of Duponol WAQE (1.5 g per liter) and adjusted with diliite sodium carbonate to a pH of 10+ 0.1. The specimen was then removed, ri:nsed thoroughly under tap water, de-watered by squeezing and airdried. The dry carpet specimen was then tested according to the stain test described above.

UV Lightfastness Colorfastness to UV light was measured according to AATCC Test Method 16E-1987. The specimens were rated after exposure to 40 AATCC Fading Units (AFU) with the Gray Scale for color change.

NO, Lightfastness Colorfastness to oxides of nitrogen was carried out according to AATCC Test Method 164-1987. At the end of 2 cycles the specimens were rated to the Gray Scale for color change.

Treatment in accordance with this invention lead to stain-resistant carpets. Furthermore, carpeting washed with shampoo after application of the stain-resists of this invention, brz' before staining, still possessed a high degree of stain- resistance.

Example 1 To a solution of 649.5 g of sodium hydroxide in 5184 g of deionized water at 40 0 C was slowly added under agitation 2,500 g of an isobutylene-maleic anhydride copolymer of 10,000 moleculat weight, commercially available as "Isobam" -01 from Kuraray Corp., Japan. The exotherm during hydrolysis reached 70-90°C. The reaction mass was held about 15-20 hours 80-85 0 C before cooling to 0 C. To the clear, amber solu on was added under agitation 1457.5 g of a sulfuric acid solution which lowered the pH to 2.65. After cooling to about the amount of 1764.7 g of a sulfonated hydroxy-aromatic formaldehyde condensation product available from Ciba-Geigy Corp. as "Erional" LY was added under agitation to give 11764.8 g of a clear, brownish solution having an active ingredient content of about 25%, a pH of 2.61 and a viscosity of 286 Pa.s. Addition of 12% sulfamic acid solution to a 1% solution of Example 1 did not cause precipitation at a pH as low as Exampl 2 To a solution of 259.7 of sodium hydroxid in 2073.6 g of dionized water at 60°C was slowly added under agitation 1,000 g of an isobutylene-maleic i: hisrr WO 93/19238 PC/US93/02805 8 anhydride copolymer of molecular weight of about 40,000 and commercially available as "Isobam" -04 from Kuraray Corp., Japan. The reaction mass was agitated for 18 hours at 80-85°C. To this clear, amber liquid was then added at 0 C under stirring a solution of 683.3 g 30% sulfuric acid in 983.3 g deionized water to give a clear product having an active ingredient content of 20%, a viscosity of 606 Pa.s at a pH of 2.40. To 400 g of polymer prepared in the manner described above was added at room temperature and under agitation 80.0 g of a sulfonated hydroxyaromatic formaldehyde condensation product available from Ciba-Geigy Corp. as "Erional" LY. The clear brownish liquid had an active ingredient content of 20.8%. A 1% solution remained clear after adjusting the pH to 1.5 with dilute sulfuric acid.

ExaAple 3 To a solution of 77.9 g of sodium hydroxide in 622.1 g deionized water at 40°C was slowly added 300 g of an isobutylene-maleic anhydride copolymer of 10,000 mole-ular weight, commercially available as "Isobam" -01 from Kuraray Corp., Japan. The exotherm during hydrolysis reached 70-90 0 C. The reaction mass was held for about 15 to 20 hours at 80-85 0 C. After cooling to 60°C a solution of 208.6 g 30% sulfuric acid in 80 g deionized water was added under agitation to give 1288.6 g of a clear, amber solution having 23.3% of active 2 0 ingredients, a pH of 2.47 and a viscosity of 340 Pa.s. To 364.8 g polymer prepared in the manner described above was added to room temperature under agitation g of a sulfonated hydroxyaromatic formaldehyde condensation product available from Cybron Chemicals as "Stainfree" (30% active ingredients) to give a clear brownish product having an active ingredient content of about 24.1%. This material remained clear when applied at a pH of 2.0 at any desired concentration.

Example 4 To 364.8 g of the polymer used in Example 3 was added under agitation at room temperature 50 g of a sulfonated hydroxyaromatic formaldehyde condensate available from Allied Colloid Co. as "Algard" NS (30% active ingredients) to give a clear brownish liquid having an active ingredient content of about 24.1%. This material remained clear at a pH of 2.0 at any desired concentration.

Example To a solution of 26.0 g of sodium hydroxide in 207.4 g of deionized water was slowly added at 50°C under stirring 100 g of an isobutylene-maleic anhydride copolymer having a molecular weight of 10,000 and commercially i i pr WO 93/19238 PCT/US93/02805 9 available as "Isobam"-01 from Kuraray Co., Japan. A solution of 58.8 g of a sulfonated hydroxyaromatic formaldehyde condensate available from Bayer AG. as "MESITOL" NBS (30% active ingredients) and 24.7 g of a 30% sodium hydroxide solution in 759.3 g of deionized water was added under stirring to give 1176.2 g of a clear, brownish liquid at a pH of 8.55 and an active ingredient content of 10.0%. A 1% solution remained clear after adjusting the pH to 2.0 with dilute sulfamic acid.

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Claims (26)

1. 2. A composition according to Claim 1 wherein said weight ratio is in the range between about 90:10 and 10:90.
2. 3. A composition according to Claim 1 wherein said weight ratio is in the range between about 60:40 and 40:60.
3. 4. A composition according to any one of Claims 1 to 3 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular S_ weight of about 700 to 200,000. A composition according to Claim 4 wherein at least 95 wt% of said I maleic anhydride polymers have a number average molecular weight of about 1,000 to 100,000. 25, 6. A composition according to any one of Claims 1 to 5 wherein said t polymer contains about one polymer unit derived from maleic anhydride per polymer unit derived from one or more alpha-olefin monomers.
4. 7. A composition according to any one of Claims 1 to 6 wherein at least one of said 1-alkenes is isobutylene.
5. 8. A composition according to any one of Claims 1 to 7 wherein up to weight of said alpha-olefin is replaced by one or more of C, to C 4 alkyl ~AL 4 C.) 5/9/95MSAP7844.SPE,10 i- i 11 acrylate or methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl sulfide, N-vinyl pyrrolidone, acrylonitrile, or acrylamide, or mixtures of the same.
6. 9. A composition according to any one of Claims 1 to 8 wherein up to 75 weight of said maleic anhydride is 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) or cycloalkyl (C3.8) esters of the foregoing acids of sulfated castor oil. A composition according to any one of Claims 1 to 8 wherein up to 30 weight of the maleic anhydride is replaced by acrylic or methacrylic acid.
7. 11. 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 alpha-olefin/maleic anhydride polymer or a mixture of said polymers wherein said polymer contains between @4 S1 5" 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 said polymer comprising between 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 (ii) 0 to 20 mol percent of at least 2 one 1-alkene containing 3 or 10 to 18 carbon atoms, and a sulfonated phenol-formaldehyde condensation product, the weight ratio of A:B being in the range between about 5:95 and 95:5.
8. 12. A substrate according to Claim 11 wherein said weight ratio is in the range between about 90:10 and 10:90.
9. 13. A substrate according to Claim 11 wherein said weight ratio is in the range between about 60:40 and 40:60.
10. 14. A substrate according to any one of Claims 11 to 13 wherein at least wt% of said maleic anhydride polymers have a number average molecular weight of about 700 to 200,000.
11. 15. A substrate according to Claim 14 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about ll 5/9/95MSAP7844.SPE,1 <Erf 12 1,000 to 100,000.
12. 16. A substrate according to any one of Claims 11 to 15 wherein said polymer contains about one polymer unit derived from maleic anhydride per polymer unit derived from one or more alpha-olefin monomers.
13. 17. A substrate according to any one of Claims 11 to 16 wherein at least one of said 1-alkenes is isobutylene.
14. 18. A substrate according to any one of Claims 11 to 17 wherein up to weight of said alpha-olefin is replaced by one or more of C, to C4 alkyl acrylate or methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl sulfide, N-vinyl pyrrolidone, acrylonitrile, or acrylamide, or mixtures of the same.
15. 19. A substrate according to any one of Claims 11 to 18 wherein up to S 75 weight of said maleic anhydride is 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) or cycloalkyl (C esters S of the foregoing acids or sulfated castor oil. A substrate according to any one of Claims 11 to 18 wherein up to weight of the maleic anhydride is replaced by acrylic or methacrylic acid.
16. 21. A process for imparting stain-resistance to a polyamide textile 2- substrate which comprises applying to said substrate together or separately in amounts effective to impart stain-resistance to said substrate: a water-soluble or water-dispersible alpha-olefin/maleic I anhydride polymer or a mixture of said polymers wherein said polymer contains 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 said polymer comprising between 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 (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or 10 to 18 carbon atoms, and a sulfonated phenol-formaldehyde cn,,densation product, the weight ratio of A:B being in the range between about 5:95 and 95:5. 5/995MSAP7844.SP,12 4-' 13 weight ratio of A:B being in the range between about 5:95 and 95:5.
17. 22. A process according to Claim 21 wherein said weight ratio is in the range between about 90:10 and 10:90.
18. 23. A process according to Claim 21 wherein said weight ratio is in the range between about 60:40 and 40:60.
19. 24. A process according to any one of Claims 21 to 23 wherein at least wt% of said maleic anhydride polymers have a number average molecular weight of about 700 to 200,000. A process according to Claim 24 where in at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 1,000 to 100,000.
20. 26. A process according to any one of Claims 21 to 25 wherein said S polymer contains about one polymer unit derived from maleic anhydride per Sb polymer unit derived from one or more alpha-olefin monomers.
21. 27. A process according to Claim 26 wherein at ieast one of said 1- i alkenes is isobutylene.
22. 28. A process according to any one of Claims 21 to 27 wherein up to weight of said alpha-olefin is replaced by one or more of C 1 to C 4 alkyl acrylate or methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl -0 sulfide, N-vinyl pyrrolidone, acrylonitrile, or acrylamide, or mixtures of the same.
23. 29. A process according to any one of Claims 21 to 28 wherein up to weight of said maleic anhydride is 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 8 or cycloalkyl (C 3 8 esters of the foregoing acids or sulfated castor oil. A process according to any one of Claims 21 to 28 wherein up to weight of the maleic anhydride is replaced by acrylic or methacrylic acid.
24. 31. A composition according to Claim 1, substantially as hereinbefore described with reference to any one of the examples,
25. 32. A substrate according to Claim 11, substantially as hereinbefore 5/j995MSAP7844,SPB,13 lib -i 14 described with reference to any one of the examples.
26. 33. A process according to Claim 21, substantially as hereinbefore described with reference to any one of the examples. DATED this day of September, 1995. E I DU PONT DE NEMOURS AND COMPANY By Their Patent Attorneys: CALLINAN LAWRIE oi 4 *9 4 9O 00 444 49 #4 4 144 4$ r 4 I41 P 5/9/95MSAP7844.SP'E14 pr ITERNATIONAL SEARCH REPORT International application No. PCT/US 93/02805 A. CLASSIFICATION OF SUBJECT MATTER IPC5: D06M 15/41 D06M 15/263 D06M 15/21 According to International 11atentClassificadon or to both national Classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) D06M Documentation searched other than minimum documentation to the extent that such documents are included in the Fields searched Electronic data base consulted during the international search (name of cata base and, where practicable, search terms used) WPI, CLAIMS C, DOCUMENTS CONSIDERED TO BE RELEVANT Category'j Citation of document, with indication, where appropriate, of the relevant passages Relevant 1o Claim No. PX WO, Al, 9210605 DU PONT DE NEMOURS AND 1,4-11, COMPANY), 25 June 1992 (25.06.92), page 5, 14-17,21-27 line 14 line 21, claims 1,3-19, abstract Y WO, Al, 9102116 DU PONT DE NEMOURS AND I 1,11,21 COMPANY), 21 February 1991 (21.02.91), claim 1, I abstract Y EP, A2, 0306992 JOHNSON SON, INC.), 1,11,21 March 1989 (15.03.89) W Further documents are listed in the continuation of Box C, See patent family annex. Special categones oracted documentms: -T later document puolisbed after the international, filing daie orprnonty document defining the general state of the art which is not considered date and not in conflict With the application but cited to understand in be or particular relevance the pnnciple or theory underlying the invenoton Eentier document nut published on or after the international filing date wX document of particular relevance: the claimed invention cannot be L doumet Wsch ay hro dobts n vont clim~s orwhih ~considered novel or cannot he considered to involve an invctive cited in estalism the publication date of answher citation or other se ontedcmn ae ln special reason (as specified) ly* document of particular relevance: the claimed invention cannot be 0' document refe-ng to an oral disclosure, use, exibtion or other considered in involve an inventive step when the document is means combined with on.- or smore other sucti documents, such combination document published pnior to the international filing date but later than being obvious to a person skilled in toe art the pn-onry date claimed document member of the same patent family Date of the actual completion of the international search Date of mailing of the international search report -2 Jul 19931. 17. 93 Nnlzme and imailint addre-ss of die ISA/ Authorized officer E-uracean Patent Of-ice, P.B. S8l3 Patentlaza 2 NL-4230 H*V Rijswijkt o Tel. .70) 340.1040, Tz. It 631I epa nJl. DAGMAR JARVMAN r 3 1 7 0 13 403016 I Form PCT/ISA/210 (second sheet) (July t992) J j INTERNATIONAL SEARCH REPORT inter. .onal application No. PCT/US 93/02805 C (Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT Category* [staion of document, with indication, where appropriate, of the relevant passages RTpelevant to claim No. EP, A2, 0329899 I. DU PONT DE NEMOURS AND COMPANY), 30 August 1989 (30.08.89) 1, 11,21 Form PCT/ISA/2 10 (continuatuon of second sheet) (July 1992) SA 013 Patent document Publicauon Patent family Publication WO-Al- 9210605 25/06/92 AU-A- 9157391 08/07/92 WO-Al- 9102116 21/02/91 AU-B- 632159 17/12/92 AU-A- 6163290 11/03/91 EP-A- 0437583 24/07/914 JP-T- 4501147 27/02/92 US-A- 5057121 15/10/91 EP-A2- 0306992 15/03/89 AU-A- 2206388 16/03/89 JP-A- 1138212 31/05/89 US-A- 4871823 03/10/89 EP-A2- 0329899 30/08/89 AU-A- 2708988 15/06/89 ~JP-A- 2138365 28/05/90 US-A- 5001004 19/03/91 Form PCT.IS A;210 (patent family annex) (July 1992)