CA2132731C

CA2132731C - Stain resists for polyamide substrates

Info

Publication number: CA2132731C
Application number: CA002132731A
Authority: CA
Inventors: Engelbert Pechhold
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1992-03-25
Filing date: 1993-03-25
Publication date: 2006-06-20
Anticipated expiration: 2013-03-25
Also published as: JP3271766B2; MX9301644A; DE69300635T2; WO1993019238A1; JPH07505450A; AU664268B2; EP0632856B1; CA2132731A1; AU3935393A; DE69300635D1; EP0632856A1

Abstract

A stain-resist for polyamide textiles comprises blends of maleic anhydride/alpha-olefin polymers with sulfonated phenol-formaldehyde-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.

Description

Title Stain-Resists for Polvamide Substrates Field of the Invention The present invention relates to polymeric stain-resist compositions.
Back-0round of the Invention 1o Polyamide substrates, such as nylon carpeting, upholsten~ fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages. ,An especially troublesome staining agent is FDIC Red Dye No. 40, commonly found in soft drink preparations. Different t<Pes of treatments have been proposed to deal W th staining problems. One approach is to apply a composition containing a sulfonated phenol-formaldehyde condensation product to the substrate. However, sulfonated phenolformaldehvde condensation products are themselves subject to discoloration; commonly they turn yellow. Yellowing problems are described by V'.
H. Hemmpel in a March 19, 1932 article in America's Textiles, entitled 'Reversible Z'ellov~~ing Not Finisher's Fault". Hemmpel attributes yellowing to exposure of a 2 0 phenol-based finish to nitrogen oa:ides 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. U.S. Patent Nos. 5,707,708 and 5,834,088 disclose and claim polyamide fibrous substrates treated with water-soluble or water-dispersible malefic 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 U.S. Patent No. 5,460,887.
Brief Summan~ of the Invention The present invention provides a composition useful for imparting stain resistance to a polvamide fibrous substrate comprising (i) a water-soluble or v~ater-dispersible alpha-olefin/maleic anhydride polymer or a mixture of said polymers ; and .. ,.. ,.., ..~.." CA 02132731 2004-06-08 Yl. 1 / l..'''!3/U2~U~
(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 acent which improves the wet-fastness of dyeing on polvamide fibers.
The compositions of the present invention show enhanced durahiliy to shampoo washing of polyamide substrates treated with the compositions. In addition, the invention provides stain resists which are more resistant to vellowin~
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 to 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 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-solubilit)~.
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 malefic anhydride copolymer to resin may lie in the range of between about 9~:5 and 5:9~, preferably between 2 o 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 more preferably 1.5 to 2.5 with acid. Surprisingly the stain-resistant compostion of the present invention remains clear at such low pH. This finding is advantageous since the stain-resistant compostion 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 malefic anhydride /alpha-olefin poi~zner The polymers useful for the purposes of this invention comprise one 3 0 or more water-soluble or water-dispersible hydrolyzed malefic 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 18 carbon acorns, such as butadiene, chloroprernc:, isoprene, and methyl-1,5-hexadiene; 1-alkenes containing 4 to fi carbon atoms, such ac :35 isobutylene, 1-butene, 1-hexene, 1-octene, and the like, W th isobutvlene beings nrcw preferred. A part of the alpha-olefins can be replaced by other monomers, e.g., up nV 7J/ 1 yLJ(1 CA 02132731 2004-06-08 ('~. I / u~yJ/ ULeU
to 50 wt~io of allyl (C1_4) acrylates, alkyl (C1_4) methacn~lates, vinyl sulfides, N-vinyl pyrrolidone, acrylonitrile, acrylamide, as well as mixture of the same.
A part (preferably 1-75 is by weight) of the malefic anhydride can he replaced by maleimide. N-all,~~l (C1_4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alhwl (C1_lg) esters of the foregoing acids, cycloalkyl (C3-g) esters of the foregoing acids.
sulfated castor oil, or the like. At least 95 wt% of the malefic anhydride co-or terpolvmers have a number average molecular weight of in the range between ahout 700 and 200.000, preferably between about 1,000 and 100,000.
to The malefic anhydride polymers useful in the present invention can be prepared according to methods well-knovyn in the art. The malefic 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 allyl alcohol to provide polymeric alpha-olefin/maleic acid monoesters, which have stainblockin~
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 malefic anhydride. The alpha-olefin content of the polymers of this invention comprise between (a) 100 and 80 mol~'c of 2 o 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 malefic 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. 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°C.
The polymers suitable for the purposes of this invention can be prepared by hydrolyzing the malefic anhvdride/olefin polymers according to 3 5 methods well-known in the art. For example, they can be hydrolyed to the free acid or their salts by reaction W th water or alkali.

V~'O 93/19238 CA 02132731 2004-06-08 p~-/~~~93/0280~

Suitable malefic anhydride polymers can conveniently obtained by hydrolysis of "Isobam"-O1, an isobutylene malefic anhydride copolymer of molecular weight around 10,000, "Isobam"-04 a sinular polymer hacking 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 malefic 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 W thout further treating is "Lindron" 10 (ex Lindau Chemical), a butadiene/maleic anhydride 1o copolymer having a molecular weight of about 5,000 to 10,000. Other suitable copolymers include monoesters of C4_g 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-~ alcohols especially methanol and ethanol.
Preparation of malefic 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 SCL, Part A, Polymer Chem., 27 (12) pages 4099 to 4108.
These references 2 o contain further teaching of techniques for the preparation of such polymers.
The sulfonated~henol-formaldehyde resin The sulfonated phenol-formaldehyde condensation products which can be used for the purposes of this invention include any sulfonated hydroa~~
aromatic-formaldehyde condensation products which have been described in the 2 5 prior art as being useful as dye-resist agents or dye-fixing agents, in other words, dye-resewing agents or agents which improve wetfastness or dyeings on polyamide fibers. See for example U.S. 4,59'_',9=10, U.S. 4,591,591, U.S. 3,790,344 and GB
1,291,784, Examples'of commercially available condensation products suitable for the :3 o 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" N~'~', a product of C'iha,-C;eia, Corp., (formed by condensing a mixture of naphthalene monosulfonic acid, bis(hydroxyphenyl) sulfone and formaldehyde; U.S. Patent Number 3,716,39x) and 3 5 "Erional" LT. The sulfonated hydroxyaromatic formaldehyde products sold as r ' NV~ 93/19238 PC1'lUS93/02~0~
~~ ~1i~5~~~1 "Stainfree" by Cybron Chemicals and "Algard" htS 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 present invention can be applied to the substrate separately or together as a blend: In the ease of the present invention, stain-resi~tanc~ of polyamide substrates is slightly better if the malefic 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 mi~cture 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'~yed or untlyed polyamide textile substrates. In addition, they can be applied to such substrates in the absence or presence of a polyfluoro-organic oil-; water-, and/or soil-repellent materials: In the alternative, such a polyfluor~organic 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 2 5 compositions are applied to the textile substrate at either 20°C
followed by heat treatment at a temperature in the range between about ~O to 1S0°C for about 1 to SO minutes, or,applied at emperaturss in the range between about 40 and 95°C for about l to 60 minutes. For example; at a ply between about 2 and 3, a temperature between about 70 and ~0°C is preferred. However, stain-blocking can be obtained when application is effected even at that of cold tap water (10-15°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 farm of aqueous shampoo preparation, with or without one or more polvfluoro-organic oil-, water-, and/or soil- repellent materials. They my: be applied at the ..
w(~ 93/19238 s~ a~ PC.'f/U~93102~~~ a;;,;~%

levels described above, at temperature described, and at a p~I 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/sq yd 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 1 o described in one of the examples of pI~ 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 FW bber Co. Calhoun, GA) was applied as to carpet backing adhesive, with a secondary polypropylene backing under the trade name Actionbac (AMOCU, Atlanta, GA).
Stain 'Pest A carpet specimen (3x5 inch) was placed on a flat non-absorbent surface. 20 m1 of a solution made from 45 g of cherry-flavored, sugar sweetened, 2 0 commercially available dilutable soft drink containing FDIC Iced Dye No.
40 and 500 ml of water was poured into a 2-inch diameter cylinder which was tightly placed over the specimen. The cylinder was removed after all the liquid had been absorbed: The shined 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 vvexe visually inspected and the amount of color remaining in the stained area rated acc~rding to the following stain rating scale:

5 = no staining 4 ~ slight staining 3 = noticeable staining 3 0 2 = considerable staining 1 = heavy staining In other wards, a stain rating of 5 is excellent, showing outstanding stain resistance, whereas 1 is the worst rating comparable to an untreated control sample.

~~'';'" W~ 93/ y 923A c- , s .a PCTIUS93/02$U~
Shampoo Wash I~urabilitX,Test A 3x5 inch carpet specimen was submerged for 5 minutes at room temperature in a detergent solution consisting of I~uponol WAQE (1.5 g per liter) and adjusted with dilute sodium carbonate to a pH of 10~ 0.1. The specimen was ~ then removed, rinsed thoroughly under tap water, de-watered by squeezing and air-driedo The dry carpet specimen was then tested according to the stain test described above.
IJ~ Li,ghtfastness Colorfastness to ~JV light was measured according to AATCC Test o Method 16E-1987, The specimens were rated after exposure to 40 AATCC Fading Units (AFLJ) with the Gray Scale for color change.
NO,~Lightfastness Colorfastness to oxides of nitrogen was carried out according to r'~ATCC Test Method 1b4-1987: At the end of 2 cycles the specimens were rated to 25 the Ciray Scale for color change.
Treatment in accordance with this invention lead to stain-resistant carpets: Furthermore, carpeting gashed with shampoo after application of the stain-resists of this invention; but befare staining, still possessed a high degree of stain- resistance.
2 0 ' Example I
'~'o a solution of 649.5 g ~f sodium hydroxide in 5184 g of deionized water at 40°C was slowly added under agitation 2,500 g of an isobutylene-rnaleic anhydride copolymer of 10,p00 molecular weight, commercially available as '°Isobam'° -01 from I~u~-aray Corp.~ Japan. The exothenn duz~ing hydrolysis reached 2 5 70-90°C. The reaction mass was held about l5-~~ hours 80-85°C before cooling to 65°CTo-the eiear, amber solution was added under agitation 1457.5 g of a 30%
sulfuric acid solution which lowered the pH ito 2:65. Aftez~ cooling to about 55°C, the amount of 1764.7 g of a sulfonated hydroxy~aromatic formaldehyde condensation product available from Ciba-C~eigy Corp. as'~rional" LY was added 3 o under agitation to give 11?64.8 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 17%a sulfamic acid solution to a 1% solution of Example 1 did not cause precipitation at a pH as low as 1.5:
Exam~e 2 ~ 5 To a solution of 259.7 of sodium hydroxide in 2073.6 g 0.f dionized water at 60°C was slowly added under agitation 1,000 g of an isobutylene-malefic ~wr.r. .
~'V093/19238 a ~ ,~.~ Pf'TlLJ593/~Z~O~ ''~~:
.~'~ ~ ~~'~ s 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 Blear, amber liquid was then added at 60°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-Geigry Corp. as "ErionaI" 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.
Example 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-rnaleic anhydride i5 eapolymer of 10,000 molecular weight, commercially available as °'Isobam" -01 from I~uraray Corp., Japan. The exotherm during hydrolysis reached 70-90°C.
The reaction mass was held for about 15 to 20 hours at 80-85°C. .After cooling to 60°C a solution of 208.6 g 3t7% sulfuric acid in 80 g deionized water was added under agitation to give 1288.6 g of a clear, amber solution having 23.3%a 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 50 g of ~ sulfonated hydroxy~.romatic formaldehyde condensation product available from Cybron Chemicals as '°Stainfree" (30% active ingredients) to give a clear brownish product having an aetive ingredient content of about 24.1 %. This z.5 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" h18 (30% active 3 0 ' ingredients) to give a clear brownish liquid having an active ingredient content of ab~ut 24.1 %. This material remained clear at a pH of 2.0 at any desired concentration.
Example 5 To a solution of 26.0 g of sodium hydroxide in 207.4 g of deionized 35 water was slowly added at 50°C under stirring 100 g of an isobutylene-malefic anhydride copolymer having a molecular weight of 10,000 and commercially v W~ 93/19238 ~' ~ '.~ ~? '~ PCT/US93f0280a ..~. e1 :~;.~ ~ ;.l available as "Isobam"-O1 from I~uraray Co., Japan. A solution of 58.8 g of a sulfonated hydroxyaromatic formaldehyde condensate available from Bayer AG. as °'I~SITOL" hTBS (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 eontent of 10.d%. A
1 % solution remained Blear after adjusting the pH to 2.0 with dilute sulfamic acid.

Claims

What is claimed is:

1. A composition for imparting stain resistance to a polyamide fibrous substrate comprising:
(A) 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 (i) 100 and 80 mol percent of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated dime containing 4 to carbon atoms and (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or to 18 carbon atoms, and (B) a sulfonated phenol-formaldehyde condensation product, the weight ratio of A:B being in the range between about 5:95 and 95:5.

2. The composition of Claim 1 wherein said weight ratio is in the range between about 90:10 and 10:90.

3. The composition of Claim 1 wherein said weight ratio is in the range between about 60:40 and 40:60.

4. The composition of Claim 1 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 700 to 200,000.

5. The composition of Claim 4 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 1000 to 100,000.

6. The composition of any one of claims 1 through 5 wherein said polymer contains about one polymer unit derived from maleic anhydride per polymer unit derived from one or more alpha-olefin monomers.

7. The composition of Claim 6 wherein at least one of said 1-alkenes is isobutylene.

8. The composition of Claim 1 wherein up to 50 weight % of said alpha-olefin is replaced by one or more of C1 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.

9. The composition of Claim 1 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 or sulfated castor oil.

10. The composition of Claim 1 wherein up to 30 weight % of the maleic anhydride is replaced by acrylic or methacrylic acid.

11. A polyamide fibrous substrate having deposited on it an amount of a composition effective to impart stain-resistance to said substrate comprising:
(A) 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 (i) 100 and 80 mol percent of at least one 1-alkene containing 4 to 8 carbon atoms or terminally unsaturated diene containing 4 to carbon atoms and (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or to 18 carbon atoms, and (B) a sulfonated phenol-formaldehyde condensation product, the weight ratio of A:B being in the range between about 5:95 and 95:5.

12. The substrate of Claim 11 wherein said weight ratio is in the range between about 90:10 and 10:90.

13. The substrate of Claim 11 wherein said weight ratio is in the range between about 60:40 and 40:60.

14. The substrate of Claim 11 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 700 to 200,000.

15. The substrate of Claim 14 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 1000 to 100,000.

16. The substrate of any one of Claims 11 through 15 wherein said polymer contains about one polymer unit derived from maleic anhydride per polymer unit derived from one or more alpha-olefin monomers.

17. The substrate of Claim 16 wherein at least one of said 1-alkenes is isobutylene.

18. The substrate of Claim 11 wherein up to 50 weight % of said alpha-olefin is replaced by one or more of C1 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.

19. The substrate of Claim 11 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 or sulfated castor oil.

20. The substrate of Claim 11 wherein up to 30 weight % of the maleic anhydride is replaced by acrylic or methacrylic acid.

21. A process for imparting stain-resistance to a polyamide textile substrate which comprises applying to said substrate together or separately in amounts effective to impart stain-resistance to said substrate:
(A) 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 dime containing 4 to carbon atoms and (ii) 0 to 20 mol percent of at least one 1-alkene containing 3 or to 18 carbon atoms, and (B) a sulfonated phenol-formaldehyde condensation product, the weight ratio of A:B being in the range between about 5:95 and 95:5.

22. The process of Claim 21 wherein said weight ratio is in the range between about 90:10 and 10:90.

23. The process of Claim 21 wherein said weight ratio is in the range between about 60:40 and 40:60.

24. The process of Claim 21 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 700 to 200,000.

25. The process of Claim 24 wherein at least 95 wt% of said maleic anhydride polymers have a number average molecular weight of about 1000 to 100,000.

26. The process of any one of Claims 21 through 25 wherein said polymer contains about one polymer unit derived from maleic anhydride per polymer unit derived from one or more alpha-olefin monomers.

27. The process of Claim 26 wherein at least one of said 1-alkenes is isobutylene.

28. The process of Claim 21 wherein up to 50 weight % of said alpha-olefin is replaced by one or more of C1 to C4 allyl acrylate or methacrylate, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl sulfide, N-vinyl pyrrolidone, acrylonitrile, or acrylamide, or mixtures of the same.

29. The process of Claim 21 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 or sulfated castor oil.

30. The process of Claim 21 wherein up to 30 weight % of the maleic anhydride is replaced by acrylic or methacrylic acid.