COMPOSITIONS WITH FREEZE THAW STABILITY

• US 20110223125A1
• Filed: 02/14/2011
• Published: 09/15/2011
• Est. Priority Date: 02/12/2010
• Status: Active Grant

• Current Assignee: Specialty Operations France
• Original Assignee: Rhodia Operations (Solvac SA)
• Inventors: HENNAUX, Pierre, O'ROURKE, Mary, PARK, Ericka, HERVE, Pascal, BZDUCHA, Wojciech, HOUGH, Lawrence Alan
• Granted Patent: US 9,080,135 B2
• Time in Patent Office: Days
• US Class Current: 424/70.12
• CPC Class Codes: A61K 2800/52 Stabilizers
• CPC Class Codes: A61K 8/8152 Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• CPC Class Codes: A61K 8/86 Polyethers
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: A61Q 19/10 Washing or bathing preparations
• CPC Class Codes: C08F 220/288 and containing polypropylene-co-ethylene oxide in the alcohol moiety
• CPC Class Codes: C08F 220/306 and polyethylene oxide chain in the alcohol moiety
• CPC Class Codes: C08F 283/065 on to unsaturated polyethers, polyoxymethylenes or polyacetals
• CPC Class Codes: C08F 290/062 Polyethers
• CPC Class Codes: C09K 8/68 containing organic compounds
• CPC Class Codes: C09K 8/685 containing cross-linking agents
• CPC Class Codes: C09K 8/88 macromolecular compounds
• CPC Class Codes: C09K 8/887 containing cross-linking agents
• CPC Class Codes: C11D 17/0026 Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
• CPC Class Codes: C11D 3/37 Polymers polymeric surface-active agents C11D1/008; polysaccharides C11D3/222
• CPC Class Codes: C11D 3/3707 Polyethers, e.g. polyalkyleneoxides
• CPC Class Codes: C11D 3/3765 in liquid compositions
• CPC Class Codes: C11D 3/3773 in liquid compositions

Abstract

Composition including freeze thaw stability polymer such as a copolymer having a weight average molecular weight of at least about 30,000 grams per mole, a blend of a first polymer and a second polymer, a crosslinked alkali swellable acrylate copolymer, or at least one polymerizable reactive alkoxylated acrylate monomer. The copolymer has one or more first monomeric units and one or more second monomeric units. The one or more first monomeric units each independently including at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit. The bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom. The one or more second monomeric units each independently including at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit. The first and second monomeric units do not both have branched (C₅-C₅₀)alkyl-polyether group.

Claims

1. A freeze thaw stable composition with improved freeze thaw stability, comprising:

a continuous phase comprising;

a freeze thaw stability polymer selected from at least one member of the group consisting of;

a copolymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole,

a blend of a first polymer and a second polymer,

a crosslinked alkali swellable acrylate copolymer, and

at least one polymerizable reactive alkoxylated acrylate monomer;

A. said copolymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole comprising;

(a) one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom,

(b) one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, provided that the first and second monomeric units cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group, and

(c) at least one polymerizable functional group per molecule of copolymer,

B. said blend of said first polymer comprising one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom at least one polymerizable functional group per molecule of first polymer, and said second polymer comprising one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, provided that the first and second monomeric units each have a weight average molecular weight of greater than or equal to about 30,000 grams per mole and cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group, and at least one polymerizable functional group per molecule of second polymer;

C. said crosslinked alkali swellable acrylate copolymer comprising from about 20% to about 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid, or combinations thereof;

from about 80% to about 15% by weight of at least one alpha, beta-ethylenically unsaturated monomer; and

from about 0.01 to about 5% by weight of at least one polyunsaturated compound useful in forming a partially or substantially crosslinked three dimensional network,

wherein the at least one alpha, beta-ethylenically unsaturated monomer

has the formula;

CH₂═

CXY, wherein X is H and Y is —

COOR, —

C₆H₄R′

, —

CN, —

CONH₂, —

Cl, —

NC₄H₆O, NH(CH₂)₃COOH, —

NHCOCH₃, —

CONHC(CH₃)₃, —

CO—

N(CH₃)₂;

or X is CH₃ and Y is —

COOR, —

C₆H₄R′

, —

CN, or —

CH═

CH₂;

or X is Cl and Y is Cl, wherein R is C₁-C₁₈ alkyl, or hydroxy C₂-C₁₈ alkyl, R′

is H or C₁-C₁₈ alkyl;

or

has the formula;

CH₂═

CH(OCOR₁), wherein R₁ is C₁-C₁₈ alkyl;

or

has the formula;

CH₂═

CH₂ or CH₂═

CHCH₃; and

D. said at least one polymerizable reactive alkoxylated acrylate monomer having the structural formula selected from the group consisting of structural formula IA or structural formula IB;

2. The composition of claim 1, comprising the additive, wherein the additive comprises a water insoluble additive selected from the group consisting of:

personal care benefit agents selected from the group consisting of oil, mica, exfoliation beads, emollients, moisturizers, pearlizing agent, a silicone hair conditioning agent, an antidandruff ingredient, a glycol emulsifier;

hydraulic fracturing proppant; and

home care additives selected from the group consisting of soil release agents, binders and fragrances.

3. The composition of claim 1, wherein the polymerizable functional group is selected from at least one member of the group consisting of acrylo, methacrylo, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α

-alkenyl, maleimido, styrenyl, and α

-alkyl styrenyl groups.

4. The composition of claim 1, wherein the freeze thaw stability polymer comprises:

(a) the one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom, and

(b) the one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit,

the polymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole.

5. The composition of claim 4, wherein the one or more second monomeric units, each independently comprise at least one pendant linear (C₅-C₅₀)alkyl-polyether group per monomeric unit.

6. The composition of claim 1, wherein the polymer comprises:

(a) the one or more first monomeric units, each independently comprising at least one branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, and

(b) the one or more second monomeric units, each independently comprising at least one pendant linear (C₅-C₅₀)alkyl-polyether group per monomeric unit,

the polymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole.

7. The personal care composition of claim 1, comprising the bicycloheptyl-, or bicycloheptenyl- or branched (C₅-C₄₂)alkyl-polyether radical according to structure (I):

R¹³-R¹²-R¹¹ 

 

(I)

wherein;

R¹¹ is bicycloheptyl, bicycloheptenyl, or branched (C₅-C₄₂)alkyl wherein the bicycloheptyl- or bicycloheptenyl-polyether radical may optionally be substituted on one or more of the ring carbon atoms by one or two (C1-C6)alkyl groups per ring carbon atom,

R¹² is absent or is a bivalent linking group, and

R¹³ is a bivalent polyether group.

8. The composition of claim 1, wherein the at least one polymerizable functional group per molecule of polymer comprises at least one third monomeric unit selected from the group consisting of ethylenically unsaturated carboxylic acid monomeric units, ethylenically unsaturated dicarboxylic acid monomeric units, ethylenically unsaturated alkyl monoesters of dicarboxylic acid monomeric units, ethylenically unsaturated sulphonic acid monomeric units, and ethylenically unsaturated phosphonic acid monomeric units;

ethylenically unsaturated anhydride or acid chloride monomeric units, such as maleic anhydride, may be used and subsequently hydrolyzed, salts of any thereof, and mixtures of any thereof.

9. The composition of claim 1, wherein the at least one polymerizable functional group per molecule of polymer comprises at least one fourth monomeric unit selected from the group consisting of (meth)acrylic ester monomeric units, (meth)acrylamide monomeric units, vinyl ester monomeric units, and vinyl ether monomeric units, and ethylenically unsaturated aryl monomeric units.

10. The composition of claim 1, wherein the polymer consists of a crosslinked polyacrylate microgel.

11. The composition of claim 1, wherein at least one monomeric unit comprises of Ethylene Oxide (EO) and/or Propylene Oxide (PO) connecting the hydrophobic first monomeric units and second monomeric units to a backbone of the polymer as side chains.

12. The composition of claim 1, wherein the composition comprises a structured surfactant composition comprising a surfactant phase having an ordered structure;

said composition comprising, based on 100 parts by weight of the composition;

(a) 0.5 to 40 parts by weight of total composition of at least one anionic surfactant,

(b) at least one surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, non-ionic surfactants, and cationic surfactants,

wherein the total amount of surfactants (a) and (b) is from about 10 to about 40 parts by weight, and

(c) from greater than 0 to about 30 parts by weight of electrolyte in an amount effective to, in combination with components (a) and (b) to provide a structured surfactant composition that comprises a surfactant phase having an ordered structure.

13. The composition of claim 12, wherein the composition comprises, based on 100 parts by weight of the composition:

(a) from greater than 0.5 to 40 parts by weight of the at least one anionic surfactant, and

(b) from greater than 0 to about 25 parts by weight of surfactant selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, non-ionic surfactants, and cationic surfactants, and

(c) from greater than 0 to about 30 parts by weight of electrolyte, in an amount effective to, in combination with components (a) and (b), provide a structured surfactant composition having an opaque visual appearance and exhibiting a yield strength of greater than 0 Pascals.

14. The personal care composition of claim 13, comprising

(a) from about 2 to about 40 parts by weight of the at least one anionic surfactant,

(b) 0.2 to about 10 parts by weight of the at least one surfactant selected from the group consisting of amphoteric surfactants and zwitterionic surfactants, and

(c) from 0 to about 6 parts by weight of the electrolyte.

15. The composition of claim 14, comprising, based on 100 parts by weight of the composition:

(a) from about 2 to about 40 parts by weight of at least one anionic surfactant,

(b) 0.2 to about 10 parts by weight of one or more surfactants selected from amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, and

(c) from 0 to about 6 parts by weight of electrolyte in an amount effective to, in combination with components (a) and (b), provide a structured surfactant composition having an opaque visual appearance and exhibiting a yield strength of greater than 0 Pascals,

(d) up to about 2 parts by weight of a freeze thaw agent selected from hydrocolloid polymers and mixtures thereof, and

(e) optionally from about 1 parts by weight to about 40 parts by weight, of a benefit agent selected from skin conditioning oils and mixtures thereof.

16. The composition of claim 1, wherein the composition has less than a 40% loss in initial viscosity after 3 freeze thaw cycles, the initial viscosity being at least 100 cp, preferably greater than 1000 cp;

the freeze thaw cycle comprising the steps of maintaining the composition for 12 hours at 25°

C. and then 12 hours at −

10°

C. to result in a composition having a stable freeze thaw viscosity;

the initial viscosity and the freeze thaw viscosity measured at an RPM above described in the present specification by a Brookfield viscometer using a spindle having a size above described in the present specification.

17. The composition of claim 1, wherein the composition is for cleaning hair or skin and comprises:

the polymer,

at least one detersive surfactant, and

at least one member of the group consisting of oil, mica, exfoliation beads, emollients, moisturizers, pearlizing agent, a silicone hair conditioning agent, an antidandruff ingredient, a glycol emulsifier provided that a 10% aqueous solution of said composition has a pH from about 4 to about 12.

18. The composition of claim 1, wherein the composition is a shampoo composition comprising a personal care benefit agent comprises one or more hair conditioning oils, one or more hair benefit agents other than a hair conditioning oil, or one or more hair conditioning oils and one and more hair benefit agents other than a hair conditioning oil.

19. The composition of claim 1, comprising, based on 100 parts by weight of the composition, from about 0.1 parts by weight to about 20 parts by weight of a benefit agent selected from hair conditioning oils and mixtures thereof, further comprises from about 0.01 parts by weight to about 5 parts by weight of a benefit agent selected from hair benefit agents other than hair conditioning oils and mixtures thereof.

20. The composition of claim 1, comprising:

water;

a surface active agent,

at least one personal care benefit agent, wherein at least one said personal care benefit comprises a water insoluble additive (oil, mica, exfoliation beads), and

a blend of;

(a) the first polymer comprising one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom, having a weight average molecular weight of greater than or equal to about 30,000 grams per mole, and

(b) the second polymer comprising one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, having a weight average molecular weight of greater than or equal to about 30,000 grams per mole polymer,

wherein the first and second polymers each further comprise at least one polymerizable functional group per molecule of polymer, and

the first and second monomeric units cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group.

21. The composition of claim 1, wherein the surfactant of the composition consists of at least 90 wt. % linear anionic surfactants and at most 10 wt. % branched surfactants.

22. The composition of claim 1, further comprising at least one polysaccharide selected from the group consisting of cationic polysaccharides, non-ionic polysaccharides, amphoteric polysaccharides, zwitterionic polysaccharides, hydrophobically substituted polysaccharides, and anionic polysaccharides may be employed.

26. A method for improving freeze thaw stability, comprising forming the composition of claim 1.

28. A method for promoting personal care comprising applying the composition of claim 1 to skin or hair of a user.

29. A treatment fluid for treating a subterranean formation comprising:

the composition of claim 1 in an amount of from about 0.01 percent to about 1 percent by weight of the fluid, wherein water and dissolved salts in an amount of greater than 50 parts per thousand by weight of the fluid.

30. The treatment fluid of claim 29, further comprising proppant.

31. The treatment fluid of claim 29, further comprising a surfactant.

32. A method for treating a subterranean formation comprising injecting the treatment fluid of claim 29 into the subterranean formation.

33. A home care or industrial cleaning composition for cleaning fabrics or hard surfaces comprising, the composition of claim 1 and a surfactant and a home care or industrial cleaner benefit agent.

34. A method for cleaning a substrate selected from the group consisting of a hard surface and a fabric, comprising applying the composition of claim 33 to the substrate.

23. A freeze thaw stable cosmetic composition for removing makeup from the skin and/or eyes, and/or for the cleansing thereof, comprising:

a cosmetically acceptable vehicle or carrier comprising a continuous phase comprising a fatty phase and a water-containing aqueous phase, and

a cosmetically acceptable freeze thaw stability polymer selected from the group consisting of;

a copolymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole,

a blend of a first polymer and a second polymer,

a crosslinked alkali swellable acrylate copolymer, and

at least one polymerizable reactive alkoxylated acrylate monomer;

A. said copolymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole comprising;

(a) one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom,

(b) one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, provided that the first and second monomeric units cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group, and

(c) at least one polymerizable functional group per molecule of polymer,

B. said blend of said first polymer comprising one or more first monomeric units, each independently comprising at least one bicycloheptyl-polyether, bicycloheptenyl-polyether or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom at least one polymerizable functional group per molecule of first polymer, and said second polymer comprising one or more second monomeric units, each independently comprising at least one pendant linear or branched (C₅-C₅₀)alkyl-polyether group per monomeric unit, provided that the first and second monomeric units each have a weight average molecular weight of greater than or equal to about 30,000 grams per mole and cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group, and at least one polymerizable functional group per molecule of second polymer;

C. said crosslinked alkali swellable acrylate copolymer comprising from about 20% to about 80% by weight of at least one carboxylic acid monomer comprising acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid, or maleic acid, or combinations thereof;

from about 80% to about 15% by weight of at least one alpha, beta-ethylenically unsaturated monomer; and

from about 0.01 to about 5% by weight of at least one polyunsaturated compound useful in forming a partially or substantially crosslinked three dimensional network,

wherein the at least one alpha, beta-ethylenically unsaturated monomer

has the formula;

CH₂═

CXY, wherein X is H and Y is —

COOR, —

C₆H₄R′

, —

CN, —

CONH₂, —

Cl, —

NC₄H₆O, NH(CH₂)₃COOH, —

NHCOCH₃, —

CONHC(CH₃)₃, —

CO—

N(CH₃)₂;

or X is CH₃ and Y is —

COOR, —

C₆H₄R′

, —

CN, or —

CH═

CH₂;

or X is Cl and Y is Cl, wherein R is C₁-C₁₈ alkyl, or hydroxy C₂-C₁₈ alkyl, R′

is H or C₁-C₁₈ alkyl;

or

has the formula;

CH₂═

CH(OCOR₁), wherein R₁ is C₁-C₁₈ alkyl;

or

has the formula;

CH₂═

CH₂ or CH₂═

CHCH₃; and

D. said at least one polymerizable reactive alkoxylated acrylate monomer having the structural formula selected from the group consisting of structural formula IA or structural formula IB;

24. The makeup remover/skin cleanser cosmetic composition of claim 23, wherein the cosmetically acceptable vehicle comprises the fatty phase and the aqueous phase, and

comprises from 1% to 5% by weight of (a) the polyethylene glycol diester selected from the group consisting of polyethylene glycol distearate, polyethylene glycol dipalmitate, polyethylene glycol dioleate and polyethylene glycol dibehenate and from 0.5% to 5% by weight of the freeze thaw stability polymer.

25. A composition with improved freeze thaw stability, comprising:

water;

a surface active agent;

at least one personal care benefit agent, wherein the personal care benefit is a water insoluble additive (oil, mica, exfoliation beads), and

a copolymer made by copolymerization of a mixture of monomers, said mixture comprising;

(a) one or more first monomers, each independently selected from monomers that comprise a reactive functional group and at least one bicycloheptyl-polyether, bicycloheptenyl-polyether, or branched (C₅-C₅₀)alkyl-polyether group per molecule, wherein the bicycloheptyl-polyether or bicycloheptenyl-polyether group may optionally be substituted on one or more ring carbon atoms by one or two (C₁-C₆)alkyl groups per carbon atom, and

(b) one or more second monomers, each independently selected from monomers that comprise a reactive functional group and at least one pendant straight or branched (C₅-C₅₀)alkyl-polyether group per molecule and that are copolymerizable with the first monomer, provided that the first and second monomers cannot both comprise a branched (C₅-C₅₀)alkyl-polyether group polymer,

(c) one or more third monomers providing at least one polymerizable functional group per molecule of polymer.

the copolymer having a weight average molecular weight of greater than or equal to about 30,000 grams per mole.

27. A method for improving freeze thaw stability, comprising forming the composition of claim 25.