Polymers and their use

• US 6,903,208 B2
• Filed: 08/22/2002
• Issued: 06/07/2005
• Est. Priority Date: 08/31/2001
• Status: Expired due to Fees

• Current Assignee: Henkel IP & Holding GmbH (Henkel AG & Co KGaA)
• Original Assignee: Unilever Home & Personal Care Usa Division Of Conopco, Inc.
• Inventors: Jones, Christopher Clarkson, Kukulj, Dax, Findlay, Paul Hugh
• Primary Examiner(s): Wilson, James O.
• Assistant Examiner(s): Krishnan, Ganapathy
• Application Number:
  US10/225,863
• Publication Number:
  US 20030162688A1
• Time in Patent Office: 1,020 Days
• Field of Search: 536/53, 536/116, 536/120, 536/55.1, 536/56, 536/123.1, 510/515, 510/470, 510/471, 510/473
• US Class Current: 536/55.1
• CPC Class Codes: A61K 8/893 modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C08B 15/05 Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur esters or phosphorous acids C08B5/00
• CPC Class Codes: C08B 3/16 Preparation of mixed organic cellulose esters , e.g. cellulose aceto-formate or cellulose aceto-propionate
• CPC Class Codes: C08B 3/22 Post-esterification treatments, including purification
• CPC Class Codes: C08L 1/00 Compositions of cellulose, modified cellulose or cellulose derivatives
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 3/00 Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
• CPC Class Codes: C08L 5/00 Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• CPC Class Codes: C11D 3/222 Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• CPC Class Codes: C11D 3/3788 Graft polymers

Abstract

A substituted polysaccharide comprising β_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains.

Claims

1. A substituted polysaccharide comprising β

_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains;

wherein the silicone chain(s) is or are independently selected from those of formula;

wherein L is absent or is a linking group and one or two of substituents G¹-G³ is a methyl group, the remainder being selected from groups of formula

 

the —

Si(CH₃)₂O—

groups and the —

Si(CH₃O)(G⁴)- groups being arranged in random or block fashion;

wherein n is from 5 to 1000, and m is from 0 to 100,

G⁴ is selected from groups of formula;

—

(CH₂)_p—

CH₃, where p is from 1 to 18

—

(CH₂)_q—

NH—

(CH₂)_r,—

NH₂where q and r are independently from 1 to 3

—

(CH₂)_s—

NH₂, where s is from 1 to 3

 

where t is from 1 to 3

—

(CH₂)_u—

COOH, where u is from 1 to 10,

where v is from 1 to 10, and

—

(CH₂CH₂O)_w—

(CH₂)_xH, where w is from 1 to 150, and x is from 0 to 10;

and G⁵ is independently selected from hydrogen, groups defined above for G⁴, —

OH, —

CH₃ and —

C(CH₃)₃.

2. The substituted polysaccharide of claim 1, wherein the average degree of substitution of the silicone chain(s) is from 0.001 to 0.5.

3. The substituted polysaccharide of claim 1 wherein the substituted polysaccharide comprises only β

_1-4 linkages.

4. The substituted polysaccharide of claim 1 wherein the substituted polysaccharide comprises additional linkages.

5. The substituted polysaccharide of claim 4 wherein the substituted polysaccharide comprises β

_1-4 and β

_1-3 linkages.

6. The substituted polysaccharide of claim 5 wherein the weight ratio of β

_1-3 and β

_1-4 linkages is from 1;

100 to 1;

2.

7. The substituted polysaccharide of claim 1, where L is selected from the group consisting of amide linkages, ester linkages, ether linkages, urethane linkages, triazine linkages, carbonate linkages, amine linkages and ester-alkylene linkages.

8. The substituted polysaccharide of claim 1, wherein the chemical change is hydrolysis, perhydrolysis or bond-cleavage.

9. The substituted polysaccharide of claim 1, wherein the group(s) which undergo the chemical change comprise one or more groups attached via an ester linkage to the polysaccharide.

10. The substituted polysaccharide of claim 1, having the general formula (1):

wherein at least one or more —

OR groups of the polymer are independently substituted or replaced by silicone chains and at least one or more R groups are independently selected from groups of formulae;

wherein each R¹ is independently selected from C_1-20 alkyl, C_2-20 alkenyl and C_5-7 aryl any of which is optionally substituted by one or more substituents independently selected from C_1-4 alkyl, C_1-12 alkoxy, hydroxyl, vinyl and phenyl groups;

each R² is independently selected from hydrogen and groups R¹ as hereinbefore defined;

R³ is a bond or is selected from C_1-4 alkylene, C_2-4 alkenylene and C_5-7 arylene groups, the carbon atoms in any of these being optionally substituted by one or more substituents independently selected from C_1-12 alkoxy, vinyl, hydroxyl, halo and amine groups;

each R⁴ is independently selected from hydrogen, counter cations, and groups R¹ as hereinbefore defined;

groups R which together with the oxygen atom forming the linkage to the respective saccharide ring forms an ester or hemi-ester group of a tricarboxylic- or higher polycarboxylic- or other complex acid selected from the group consisting of citric acid, an amino acid, or a combination thereof;

and n is the number of repeat units in the polysaccharide and is selected so that the number average molecular weight of the polysaccharide is in the range of 1,000 to 200,000.

11. The substituted polysaccharide of claim 9 wherein the ester-linked group(s) is/are selected from carboxylic acid esters.

12. The substituted polyssaccharide of claims 9, wherein the ester-linked group(s) is/are independently selected from one or more of acetate, propanoate, trifluroacetate, 2-(2-hydroxy-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate, salicylate, carbamate, methylcarbamate, benzoate, gluconate, methanesulphonate, toluene sulphonate, groups and hemiester groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic, glutamic, and malic acids.

13. The substituted polysaccharide of claim 1, wherein the average degree of substitution on the saccharide rings of the groups which undergo the chemical change is from 0.1 to 3.

19. The substituted polysaccharide of claim 1 where w is from 10 to 20.

14. A method of depositing a silicone onto a substrate, the method comprising contacting in an aqueous solution, the substrate and a substituted polysaccharide comprising β

_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains; and

wherein the silicone chain(s) is or are independently selected from those of formula;

wherein L is absent or is a linking group and one or two of substituents G¹-G³ is a methyl group, the remainder being selected from groups of formula

 

the —

Si(CH₃)₂O—

groups and the —

Si(CH₃O)(G⁴)- groups being arranged in random or block fashion;

wherein n is from 5 to 1000, and m is from 0 to 100,

G⁴ is selected from groups of formula;

—

(CH₂)_p—

CH₃, where p is from 1 to 18

—

(CH₂)_q—

NH—

(CH₂)_r,—

NH₂ where q and r are independently from 1 to 3

—

(CH₂)_s—

NH₂, where s is from 1 to 3

 

where t is from 1 to 3

—

(CH₂)_u—

COOH, where u is from 1 to 10,

where v is from 1 to 10, and

—

(CH₂CH₂O)_w—

(CH₂)_xH, where w is from 1 to 150, and x is from 0 to 10;

and G⁵ is independently selected from hydrogen, groups defined above for G⁴, —

OH, —

CH₃ and —

C(CH₃)₃.

20. The method of claim 14 where w is from 10 to 20.

15. A composition comprising a substituted polysaccharide comprising β

_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains and at least one further component; and

wherein the silicone chain(s) is or are independently selected from those of formula;

wherein L is absent or is a linking group and one or two of substituents G¹-G³ is a methyl group, the remainder being selected from groups of formula

 

the —

Si(CH₃)₂O—

groups and the —

Si(CH₃O)(G⁴)- groups being arranged in random or block fashion;

wherein n is from 5 to 1000, and m is from 0 to 100,

G⁴ is selected from groups of formula;

—

(CH₂)_p—

CH₃, where p is from 1 to 18

—

(CH₂)_q—

NH—

(CH₂)_r,—

NH₂ where q and r are independently from 1 to 3

—

(CH₂)_s—

NH₂, where s is from 1 to 3

 

where t is from 1 to 3

—

(CH₂)_u—

COOH, where u is from 1 to 10,

where v is from 1 to 10, and

—

(CH₂ CH₂O)_w—

(CH₂)_xH, where w is from 1 to 150, and x is from 0 to 10;

and G⁵ is independently selected from hydrogen, groups defined above for G⁴, —

OH, —

CH₃ and —

C(CH₃)₃.

16. A composition of claim 15, in which the further component comprises a surfactant.

17. The composition of claim 15, comprising from 0.01% to 25%, by weight of the substituted polysaccharide comprising β

_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains.

21. The method of claim 15 where w is from 10 to 20.

18. A method of enhancing the softening benefit of the composition on a substrate, the method comprising the application of a substituted polysaccharide comprising β

_1-4 linkages having covalently bonded on the polysaccharide moiety thereof, at least one deposition enhancing group which undergoes a chemical change in water at a use temperature to increase the affinity of the substituted polysaccharide to a substrate, the substituted polysaccharide further comprising one or more independently selected silicone chains, onto a substrate; and

wherein the silicone chain(s) is or are independently selected from those of formula;

wherein L is absent or is a linking group and one or two of substituents G¹-G³ is a methyl group, the remainder being selected from groups of formula

 

the —

Si(CH₃)₂O—

groups and the —

Si(CH₃O)(G⁴)- groups being arranged in random or block fashion;

wherein n is from 5 to 1000, and m is from 0 to 100,

G⁴ is selected from groups of formula;

—

(CH₂)_p—

CH₃, where p is from 1 to 18

—

(CH₂)_q—

NH—

(CH₂)_r,—

NH₂ where q and r are independently from 1 to 3

—

(CH₂)_s—

NH₂, where s is from 1 to 3

 

where t is from 1 to 3

—

(CH₂)_u—

COOH, where u is from 1 to 10,

where v is from 1 to 10, and

—

(CH₂ CH₂O)_w—

(CH₂)_xH, where w is from 1 to 150, and x from 0 to 10;

and G⁵ is independently selected from hydrogen, groups defined above for G⁴, —

OH, —

CH₃ and —

C(CH₃)₃.

22. The method of claim 18 where w is from 10 to 20.