Product Details

Main > TEXTILES > Cotton > Laundry Detergent > Soil Release. > Polymer. > Poly(Amine). Modified.

Product USA. P

PATENT ASSIGNEE'S COUNTRY USA

UPDATE 07.00

PATENT NUMBER This data is not available for free

PATENT GRANT DATE 11.07.00

PATENT TITLE Cotton soil release polymers

PATENT ABSTRACT Cotton soil release polymers comprising water soluble and/or dispersible, modified polyamines having functionalized backbone moieties and improved stability toward bleach. Also, laundry detergent compositions comprising these cotton soil release polymers.

PATENT INVENTORS This data is not available for free

PATENT ASSIGNEE This data is not available for free

PATENT FILE DATE 03.11.98

PATENT CT FILE DATE 25.04.97

PATENT CT NUMBER This data is not available for free

PATENT CT PUB NUMBER This data is not available for free

PATENT CT PUB DATE 13.11.97

PATENT REFERENCES CITED This data is not available for free

PATENT PARENT CASE TEXT This data is not available for free

PATENT CLAIMS What is claimed is:

1. A laundry composition comprising:

a) from about 0.001% by weight, a water-soluble or dispersible, bleach stable, modified polyamine cotton soil release agent comprising a polyamine backbone corresponding to the formula: ##STR44## having a modified polyamine formula V.sub.(n+1) W.sub.m Y.sub.n Z said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein

i) V units are terminal units having the formula: ##STR45## ii) W units are backbone units having the formula: ##STR46## iii) Y units are branching units having the formula: ##STR47## iv) Z units are terminal units having the formula: ##STR48## wherein backbone linking R units are selected from the group consisting of C.sub.2 -C.sub.12 alkylene, --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --CH.sub.2 CH(OR.sup.2)CH.sub.2 --, --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 (OCH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, and mixtures thereof; provided that when R comprises C.sub.1 -C.sub.12 alkylene R also comprises at least one --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 (OCH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, or --CH.sub.2 CH(OR.sup.2)CH.sub.2 -unit; R.sup.1 is C.sub.2 -C.sub.6 alkylene and mixtures thereof; R.sup.2 is hydrogen, --(R.sup.1 O).sub.x B, and mixtures thereof; R.sup.3 is C.sub.1 -C.sub.12 alkylene, C.sub.3 -C.sub.12 hydroxyalkylene, C.sub.4 -C.sub.12 dihydroxy-alkylene, C.sub.8 -C.sub.12 dialkylarylene, --C(O)--, --C(O)NHR.sup.5 NHC(O)--, --C(O)(R.sup.4).sub.r C(O)--, --CH.sub.2 CH(OH)CH.sub.2 O(R.sup.1 O).sub.y R.sup.1 OCH.sub.2 CH(OH)CH.sub.2 --, and mixtures thereof; R.sup.4 is C.sub.1 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, C.sub.8 -C.sub.12 arylalkylene, C.sub.6 -C.sub.10 arylene, and mixtures thereof; R.sup.5 is C.sub.2 -C.sub.12 alkylene or C.sub.6 -C.sub.12 arylene; E units are selected from the group consisting of hydrogen, methyl, --(CH.sub.2).sub.p CO.sub.2 M, --CH(CH.sub.2 CO.sub.2 M)CO.sub.2 M, --(R.sup.1 O).sub.x B, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.p PO.sub.3 M, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.p CO.sub.2 M, --(CH.sub.2).sub.q CH(SO.sub.3 M)CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.p PO.sub.3 M, --PO.sub.3 M, --(CH.sub.2).sub.q CH(SO.sub.2 M)CH.sub.2 SO.sub.3 M, and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; k has the value from 0 to about 20; m has the value from 4 to about 400; n has the value from 0 to about 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; and

b) the balance carriers and adjunct material.

2. A composition according to claim 1 wherein the adjunct ingredients are selected from the group consisting of builders, optical brighteners, bleaches, bleach boosters, bleach activators, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.

3. A composition according to claim 1 wherein R comprises greater than about 10% --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --(CH.sub.2 CH(OH)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 OCH.sub.2 CH(OH)CH.sub.2).sub.w --, --CH.sub.2 CH(OR.sup.2)CH.sub.2 --, and mixtures thereof.

4. A composition according to claim 1 comprising a cotton soil release agent wherein E units are selected from the group consisting of methyl, --(R.sup.1 O).sub.x B, --(CH.sub.2).sub.q SO.sub.3 --M.sup.+, --CH(CH.sub.2 CO.sub.2 M)--CO.sub.2 M and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; p has the value from 1 to 6; x has the value from 1 to 100.

5. A composition according to claim 4 wherein E units are methyl, or --(R.sup.1 O).sub.x B and B units are hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.q (CHSO.sub.3 M)CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.q (CHSO.sub.2 M)CH.sub.2 SO.sub.3 M, and mixtures thereof, wherein q has the value from 0 to 3.

6. A laundry detergent composition comprising:

a) from about 0.01% to about 95% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, and ampholytic surfactants, and mixtures thereof;

b) from about 0.01 to about 10% by weight, a water-soluble or dispersible, bleach stable, modified polyamine cotton soil release agent comprising a polyamine backbone corresponding to the formula: ##STR49## having a modified polyamine formula V.sub.(n+1) W.sub.m Y.sub.n Z or a polyamine backbone corresponding to the formula: ##STR50## having a modified polyamine formula V.sub.(n-k+1) W.sub.m Y.sub.n Y'.sub.k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein

i) V units are terminal units having the formula: ##STR51## ii) W units are backbone units having the formula: ##STR52## iii) Y units are branching units having the formula: ##STR53## iv) Z units are terminal units having the formula: ##STR54## wherein backbone linking R units are selected from the group consisting of --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 (OCH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, C.sub.2 -C.sub.12 alkylene, --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --CH.sub.2 CH(OR.sup.2)CH.sub.2 -- and mixtures thereof; provided that when R comprises C.sub.1 -C.sub.12 alkylene R also comprises at least one --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 (OCH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, or --CH.sub.2 CH(OR.sup.2)CH.sub.2 -unit; R.sup.1 is C.sub.2 -C.sub.6 alkylene and mixtures thereof; R.sup.2 is hydrogen, --(R.sup.1 O).sub.x B, and mixtures thereof; R.sup.3 is C.sub.1 -C.sub.12 alkylene, C.sub.3 -C.sub.12 hydroxyalkylene, C.sub.4 -C.sub.12 dihydroxy-alkylene, C.sub.8 -C.sub.12 dialkylarylene, --CH.sub.2 CH(OH)CH.sub.2 O(R.sup.1 O).sub.y R.sup.1 O--CH.sub.2 CH(OH)CH.sub.2 --, --C(O)--, --C(O)NHR.sup.5 NHC(O)--, --C(O)(R.sup.4).sub.r C(O)--, and mixtures thereof; R.sup.4 is C.sub.1 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, C.sub.8 -C.sub.12 arylalkylene, C.sub.6 -C.sub.10 arylene, and mixtures thereof; R.sup.5 is C.sub.2 -C.sub.12 alkylene or C.sub.6 -C.sub.12 arylene; E units are selected from the group consisting of hydrogen, methyl, --(CH.sub.2).sub.p --CO.sub.2 M, --(CH.sub.2).sub.q SO.sub.3 M, --CH(CH.sub.2 CO.sub.2 M)CO.sub.2 M, --(CH.sub.2).sub.p PO.sub.3 M, --(R.sup.1 O).sub.x B, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.p CO.sub.2 M, --(CH.sub.2).sub.q --CH(SO.sub.3 M)CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.p PO.sub.3 M, --PO.sub.3 M, --(CH.sub.2).sub.q CH(SO.sub.2 M)CH.sub.2 SO.sub.3 M, and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; k has the value from 0 to about 20; m has the value from 4 to about 400; n has the value from 0 to about 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1;

c) form about 0.01 to about 95% adjunct ingredients selected from the group consisting of builders, optical brighteners, bleaches, soil release polymers, bleach boosters, bleach activators, dye transfer agents, dispersents, protease enzymes, lipase enzymes, cellulase enzymes, oxidase enzymes, amylase enzymes, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof; and

d) the balance carriers.

7. A composition according to claim 6 wherein R comprises greater than about 10% --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --(CH.sub.2 CH(OH)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 OCH.sub.2 CH(OH)CH.sub.2).sub.w --, --CH.sub.2 CH(OR.sup.2)CH.sub.2 --, and mixtures thereof.

8. A composition according to claim 6 comprising a cotton soil release agent wherein E units are selected from the group consisting of methyl, --(R.sup.1 O).sub.x B, --(CH.sub.2).sub.q SO.sub.3 --M.sup.+, --CH(CH.sub.2 CO.sub.2 M)--CO.sub.2 M and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; p has the value from 1 to 6; x has the value from 1 to 100.

9. A composition according to claim 6 wherein E units are methyl or --(R.sup.1 O).sub.x B and B units are hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.q (CHSO.sub.3 M)CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.q (CHSO.sub.2 M)CH.sub.2 SO.sub.3 M, and mixtures thereof, wherein q has the value from 0 to 3.

10. A composition according to claim 1 wherein R.sup.1 is ethylene, B units are hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, and mixtures thereof, x has the value from 15 to 25.

11. A laundry detergent composition comprising:

a) from about 0.01% to about 95% by weight, of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, and ampholytic surfactants, and mixtures thereof;

b) from about 0.01 to about 10% by weight a water-soluble or dispersible, bleach stable modified polyamine cotton soil release agent comprising a polyamine backbone corresponding to the formula: ##STR55## having a modified polyamine formula V.sub.(n+1) W.sub.m Y.sub.n Z, said polyamine backbone prior to modification having a molecular weight greater than about 200 daltons, wherein

i) V units are terminal units which have the formula: ##STR56## ii) W units are backbone units which have the formula: ##STR57## iii) Y units are branching units which have the formula: ##STR58## iv) Z units are terminal units which have the formula: ##STR59## wherein backbone linking R units are selected from the group consisting of C.sub.2 -C.sub.12 alkylene; --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --; --[CH.sub.2 CH(OR.sup.2)CH.sub.2 O].sub.z (R.sup.1 O).sub.y R.sup.1 [OCH.sub.2 CH(OR.sup.2)CH.sub.2 ].sub.w --; --CH.sub.2 CH(OR.sup.2)CH.sub.2 --; an mixtures thereof; provided when R comprises C.sub.2 -C.sub.12 alkylene at least one R unit comprises --[CH.sub.2 CH(OR.sup.2)CH.sub.2 O].sub.z (R.sup.1 O).sub.y R.sup.1 [OCH.sub.2 CH(OR.sup.2)CH.sub.2 ].sub.w --; --CH.sub.2 CH(OR.sup.2)CH.sub.2 --; or --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --; R.sup.1 is C.sub.2 -C.sub.6 alkylene, and mixtures thereof; R.sup.2 is hydrogen, --(R.sup.1 O).sub.x B, and mixtures thereof; R.sup.3 is C.sub.2 -C.sub.12 alkylene, C.sub.3 -C.sub.12 hydroxyalkylene, C.sub.4 -C.sub.12 dihydroxyalkylene, C.sub.8 -C.sub.12 dialkylarylene, CH.sub.2 CH(OH)CH.sub.2 O(R.sup.1 O).sub.y R.sup.1 OCH.sub.2 CH(OR.sup.2)CH.sub.2 -- --C(O)(R.sup.4).sub.r C(O)--, --C(O)NHR.sup.5 NHC(O)--, --C(O)--, and mixtures thereof; R.sup.4 is C.sub.2 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, C.sub.8 -C.sub.12 alkylarylene, C.sub.6 -C.sub.10 arylene, and mixtures thereof; R.sup.5 is C.sub.2 -C.sub.12 alkylene or C.sub.6 -C.sub.12 arylene; E units are selected from the group consisting of methyl, --(CH.sub.2).sub.q SO.sub.3 M; --(R.sup.1 O).sub.x B; --CH(CH.sub.2 CO.sub.2 M)CO.sub.2 M; --(C.sub.2).sub.p CO.sub.2 M; --(CH.sub.2).sub.p PO.sub.3 M; and mixtures thereof; provided when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is selected from the group consisting of hydrogen; --(CH.sub.2).sub.p CO.sub.2 M; --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.q CH(SO.sub.2 M)CH.sub.2 SO.sub.3 M; --(CH.sub.2).sub.q CH(SO.sub.3 M)CH.sub.2 SO.sub.3 M; --(CH.sub.2).sub.p PO.sub.3 M; --PO.sub.3 M; and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; m has the value from 4 to 400; n has the value 0 to 200; p has the value from 1 to 6; q has the value from 0 to 6; r has the value from 0 to 20; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1;

c) form about 0.01 to about 30% by weight of a bleach; and

d) the balance carriers.

12. A composition according to claim 11 wherein R is --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, R.sup.1 and R.sup.3 are each independently C.sub.2 -C.sub.6 alkylene, and mixtures thereof; x is from 0 to 3.

13. A composition according to claim 12 wherein each x is independently 1 or 2.

14. A composition according to claim 13 wherein R.sup.1 and R.sup.3 are each independently ethylene, n-propylene, and mixtures thereof.

15. A composition according to claim 12 wherein E is methyl, --(R.sup.1 O).sub.x B, and mixtures thereof.

16. A composition according to claim 15 wherein B is hydrogen, --SO.sub.3 M, and mixtures thereof.

17. A composition according to claim 16 wherein x is from 15-25.

18. A composition according to claim 11 further comprising from 0.01% to 10% by weight of one or more non-cotton soil release agents.

19. A composition according to claim 11 further comprising from 0.1% to about 7% by weight, of a soil dispersing agent.

20. A composition according to claim 11 further comprising greater than 0.5% by weight, of carboxy methyl cellulose.
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PATENT DESCRIPTION FIELD OF THE INVENTION

The present invention relates to cotton soil release polymers comprising water soluble and/or dispersible, modified polyamines having functionalized backbone moieties and improved stability toward bleach. The present invention also relates to laundry detergent compositions comprising cotton soil release polymers and to methods for laundering cotton articles.

BACKGROUND OF THE INVENTION

A wide variety of soil release agents for use in domestic and industrial fabric treatment processes such as laundering, fabric drying in hot air clothes dryers, and the like are known in the art. Various soil release agents have been commercialized and are currently used in detergent compositions and fabric softener/antistatic articles and compositions. Such soil release polymers typically comprise an oligomeric or polymeric ester "backbone".

Soil release polymers are generally very effective on polyester or other synthetic fabrics where the grease, oil or similar hydrophobic stains spread out and form a attached film and thereby are not easily removed in an aqueous laundering process. Many soil release polymers have a less dramatic effect on "blended" fabrics, that is on fabrics that comprise a mixture of cotton and synthetic material, and have little or no effect on cotton articles. The reason for the affinity of many soil release agents for synthetic fabric is that the backbone of a polyester soil release polymer typically comprises a mixture of terephthalate residues and ethyleneoxy or propyleneoxy polymeric units; the same or closely analogous to materials that comprise the polyester fibers of synthetic fabric. This similar structure of soil release agents and synthetic fabric produce an intrinsic affinity between these compounds.

Extensive research in this area has yielded significant improvements in the effectiveness of polyester soil release agents yielding materials with enhanced product performance and formulatability. Modifications of the polymer backbone as well as the selection of proper end-capping groups has produced a wide variety of polyester soil release polymers. For example, end-cap modifications, such as the use of sulfoaryl moieties and especially the low cost isethionate-derived end-capping units, have increased the range of solubility and adjunct ingredient compatibility of these polymers without sacrifice of soil release effectiveness. Many polyester soil release polymers can now be formulated into both liquid as well as solid (i.e., granular) detergents.

In contrast to the case of polyester soil release agents, producing an oligomeric or polymeric material that mimics the structure of cotton has not resulted in a cotton soil release polymer. Although cotton and polyester fabric are both comprised of long chain polymeric materials, they are chemically very different. Cotton is comprised of cellulose fibers that consist of anhydroglucose units joined by 1-4 linkages. These glycosidic linkages characterize the cotton cellulose as a polysaccaride whereas polyester soil release polymers are generally a combination of terephthalate and oxyethylene/oxypropylene residues. These differences in composition account for the difference in the fabric properties of cotton versus polyester fabric. Cotton is hydrophilic relative to polyester. Polyester is hydrophobic and attracts oily or greasy dirt and can easily be "dry cleaned". Importantly, the terephthalate and ethyleneoxy/propyleneoxy backbone of polyester fabric does not contain reactive sites, such as the hydroxyl moieties of cotton, that interact with stains in different manner than synthetics. Many cotton stains become "fixed" and can only be resolved by bleaching the fabric.

Until now the development of an effective cotton soil release agent for use in a laundry detergent has been elusive. Attempts by others to apply the paradigm of matching the structure of a soil release polymer with the structure of the fabric, a method successful in the polyester soil release polymer field, has nevertheless yielded marginal results when applied to cotton fabric soil release agents. The use of methylcellulose, a cotton polysaccharide with modified oligomeric units, proved to be more effective on polyesters than on cotton.

For example, U.K. 1,314,897, published Apr. 26, 1973 teaches a hydroxypropyl methyl cellulose material for the prevention of wet-soil redeposition and improving stain release on laundered fabric. While this material appears to be somewhat effective on polyester and blended fabrics, the disclosure indicates these materials to be unsatisfactory at producing the desired results on cotton fabric.

Other attempts to produce a soil release agent for cotton fabric have usually taken the form of permanently modifying the chemical structure of the cotton fibers themselves by reacting a substrate with the polysaccharide polymer backbone. For example, U.S. Pat. No. 3,897,026 issued to Kearney, discloses cellulosic textile materials having improved soil release and stain resistance properties obtained by reaction of an ethylene-maleic anhydride co-polymer with the hydroxyl moieties of the cotton polymers. One perceived drawback of this method is the desirable hydrophilic properties of the cotton fabric are substantially modified by this process.

Non-permanent soil release treatments or finishes have also been previously attempted. U.S. Pat. No. 3,912,681 issued to Dickson teaches a composition for applying a non-permanent soil release finish comprising a polycarboxylate polymer to a cotton fabric. However, this material must be applied at a pH less than 3, a process not suitable for consumer use nor compatible with laundry detergents which typically have a pH greater than 7.5.

U.S. Pat. No. 3,948,838 issued to Hinton, et alia describes high molecular weight (500,000 to 1,500,000) polyacrylic polymers for soil release. These materials are used preferably with other fabric treatments, for example, durable press textile reactants such as formaldehyde. This process is also not readily applicable for use by consumers in a typical washing machine.

U.S. Pat. No. 4,559,056 issued to Leigh, et alia discloses a process for treating cotton or synthetic fabrics with a composition comprising an organopolysiloxane elastomer, an organosiloxaneoxyalkylene copolymer crosslinking agent and a siloxane curing catalyst. Organosilicone oligomers are well known by those skilled in the art as suds supressors

Other soil release agents not comprising terephthalate and mixtures of polyoxy ethylene/propylene are vinyl caprolactam resins as disclosed by Rupert, et alia in U.S. Pat. Nos. 4,579,681 and 4,614,519. These disclosed vinyl caprolactam materials have their effectiveness limited to polyester fabrics, blends of cotton and polyester, and cotton fabrics rendered hydrophobic by finishing agents.

Examples of alkoxylated polyamines and quaternized alkoxylated polyamines are disclosed in European Patent Application 206,513 as being suitable for use as soil dispersents, however their possible use as a cotton soil release agent is not disclosed. In addition, these materials do not comprise N-oxides, a key modification made to the polyamines of the present invention and a component of the increased bleach stability exhibited by the presently disclosed compounds.

It has now been surprisingly discovered that effective soil release agents for cotton articles can be prepared from certain modified polyamines. This unexpected result has yielded compositions that are effective at providing the soil release benefits once available to only synthetic and synthetic-cotton blended fabric.

The present invention provides for soil release agents that are effective on articles that comprise cotton as well as articles that comprise blends of cotton and certain synthetic fibers. The present invention also provides for laundry detergent compositions that are solid or liquid. The solid laundry detergents may be in the form of granules, flakes, pastes, gels or laundry bars. The liquid detergents can have a wide range of viscosity and may include heavy concentrates, pourable "ready" detergents, or light duty fabric pre-treatments.

The compounds of the present invention are compatible with other laundry detergent additives and adjuncts and when formulated with polyester soil release agents, now provide soil release on all fabrics.

BACKGROUND ART

In addition to the above cited art, the following disclose various soil release polymers or modified polyamines; U.S. Pat. No. 4,548,744, Connor, issued Oct. 22, 1985; U.S. Pat. No. 4,597,898, Vander Meer, issued Jul. 1, 1986; U.S. Pat. No. 4,877,896, Maldonado, et al., issued Oct. 31, 1989; U.S. Pat. No. 4,891,160, Vander Meer, issued Jan. 2, 1990; U.S. Pat. No. 4,976,879, Maldonado, et al., issued Dec. 11, 1990; U.S. Pat. No. 5,415,807, Gosselink, issued May 16,1995; U.S. Pat. No. 4,235,735, Marco, et al., issued Nov. 25, 1980; U.K. Patent 1,537,288, published Dec. 29, 1978; U.K. Patent 1,498,520, published Jan. 18, 1978; WO 95/32272, published Nov. 30, 1995; German Patent DE 28 29 022, issued Jan. 10, 1980; Japanese Kokai JP 06313271, published Apr. 27, 1994.

SUMMARY OF THE INVENTION

The present invention relates to water soluble or dispersible, modified polyamines which provide cotton soil release benefits, comprising a polyamine backbone corresponding to the formula: ##STR1## having a modified polyamine formula V.sub.(n+1) W.sub.m Y.sub.n Z or a polyamine backbone corresponding to the formula: ##STR2## having a modified polyamine formula V.sub.(n-k+1) W.sub.m Y.sub.n Y'.sub.k Z, wherein k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 200 daltons, wherein

i) V units are terminal units having the formula: ##STR3## ii) W units are backbone units having the formula: ##STR4## iii) Y units are branching units having the formula: ##STR5## iv) Z units are terminal units having the formula: ##STR6## wherein backbone linking R units are selected from the group consisting of C.sub.1 -C.sub.12 alkylene,--(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z (R.sup.1 O).sub.y R.sup.1 O--(CH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, --CH.sub.2 CH(OR.sup.2)CH.sub.2 --, and mixtures thereof; provided that when R comprises C.sub.1 -C.sub.12 alkylene, R also comprises at least one --(R.sup.1 O).sub.x R.sup.3 (OR.sup.1).sub.x --, --(CH.sub.2 CH(OR.sup.2)CH.sub.2 O).sub.z --(R.sup.1 O).sub.y R.sup.1 O(CH.sub.2 CH(OR.sup.2)CH.sub.2).sub.w --, or --CH.sub.2 CH(OR.sup.2)CH.sub.2 --, unit; R.sup.1 is C.sub.2 -C.sub.6 alkylene and mixtures thereof; R.sup.2 is hydrogen, --(R.sup.1 O).sub.x B, and mixtures thereof; R.sup.3 is C.sub.1 -C.sub.12 alkylene, C.sub.3 -C.sub.12 hydroxyalkylene, C.sub.4 -C.sub.12 dihydroxy-alkylene, C.sub.8 -C.sub.12 dialkyl-arylene, --C(O)--, --C(O)NHR.sup.5 NH--C(O)--, --R.sup.1 (OR.sup.1)--, --C(O)(R.sup.4).sub.r C(O)--, --CH.sub.2 CH(OH)CH.sub.2 --, --CH.sub.2 CH(OH)CH.sub.2 O(R.sup.1 O).sub.y R.sup.1 O--CH.sub.2 CH(OH)CH.sub.2 --, and mixtures thereof; R.sup.4 is C.sub.1 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, C.sub.8 -C.sub.12 arylalkylene, C.sub.6 -C.sub.10 arylene, and mixtures thereof; R.sup.5 is C.sub.2 -C.sub.12 alkylene or C.sub.6 -C.sub.12 arylene; E units are selected from the group consisting of hydrogen, methyl, --(CH.sub.2).sub.p CO.sub.2 M, --(CH.sub.2).sub.q SO.sub.3 M, --CH(CH.sub.2 CO.sub.2 M)CO.sub.2 M, --(CH.sub.2).sub.p PO.sub.3 M, --(R.sup.1 O).sub.x B, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, --(CH.sub.2).sub.q SO.sub.3 M, --(CH.sub.2).sub.p CO.sub.2 M, --(CH.sub.2).sub.q CH(SO.sub.3 M)--CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.q CH(SO.sub.2 M)--CH.sub.2 SO.sub.3 M, --(CH.sub.2).sub.p PO.sub.3 M, --PO.sub.3 M, and mixtures thereof; M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance; X is a water soluble anion; k has the value from 0 to about 20; m has the value from 4 to about 400; n has the value from 0 to about 200; p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1; x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1.

The present invention also relates to laundry detergent compositions that provide a non-cotton fabric soil release benefit together with a cotton soil release benefit said compositions comprising an effective amount of non-cotton as well as cotton soil polymers. What is meant by an effective amount herein is that amount of cotton soil release polymer which is sufficient to enhance the release of oils, dirt, soil, clay and other deposits from cotton and cotton blended fabric. Typically, the laundry compositions of the present invention employ at least 0.01% by weight of one or more of the cotton soil release polymers.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (.degree.C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.

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