Title: Acid cosmetic, dermatological and pharmaceutical agents
Abstract: The invention provides acidic cosmetic, dermatological, and pharmaceutical agents comprising at least one copolymer obtainable by free-radical copolymerization of
A) acryloyldimethyltaurine and/or acryloyldimethyltaurates, B) optionally, one or more further olefinically unsaturated, noncationic comonomers, C) optionally, one or more olefinically unsaturated, cationic comonomers, D) optionally, one or more silicon-containing component(s), E) optionally, one or more fluorine-containing component(s), F) optionally, one or more macromonomers, G) the copolymerization taking place if desired in the presence of at least one polymeric additive, H) with the proviso that component A) is copolymerized with at least one component selected from one of the groups D) to G).
Patent Number: 7,025,973 Issued on 04/11/2006 to Löffler, et al.
| Inventors:
|
Löffler; Matthias (Niedernhausen, DE);
Morschhäuser; Roman (Mainz, DE)
|
| Assignee:
|
Clariant GmbH (Frankfurt, DE)
|
| Appl. No.:
|
433204 |
| Filed:
|
November 28, 2001 |
| PCT Filed:
|
November 28, 2001
|
| PCT NO:
|
PCT/EP01/13861
|
| 371 Date:
|
November 17, 2003
|
| 102(e) Date:
|
November 17, 2003
|
| PCT PUB.NO.:
|
WO02/43686 |
| PCT PUB. Date:
|
June 6, 2002 |
Foreign Application Priority Data
| Dec 01, 2000[DE] | 100 59 822 |
| Current U.S. Class: |
424/400; 424/70.16; 424/70.22; 514/937; 514/975 |
| Current Intern'l Class: |
A61K 9/08 (20060101); A61K 9/10 (20060101); A61K 9/10.7 (20060101); A61K 7/07.5 (20060101); A61K 47/32 (20060101) |
| Field of Search: |
424/7016- 7018,400,422,701.2,7022-7028,781.8
514/937-38,942,975
|
References Cited [Referenced By]
U.S. Patent Documents
| 5104645 | Apr., 1992 | Cardin et al.
| |
| 5736125 | Apr., 1998 | Morawsky et al.
| |
| 5981615 | Nov., 1999 | Meijs et al.
| |
| 6054138 | Apr., 2000 | Trebosc et al.
| |
| 6120780 | Sep., 2000 | Dupuis et al.
| |
| 6123960 | Sep., 2000 | Favre et al.
| |
| 6149900 | Nov., 2000 | Afriat et al.
| |
| 6833419 | Dec., 2004 | Morschhauser et al.
| |
| 2003/0108497 | Jun., 2003 | Chevalier.
| |
| 2004/0024154 | Feb., 2004 | Schinabeck.
| |
| 2004/0141937 | Jul., 2004 | Loeffler.
| |
| Foreign Patent Documents |
| WO 96/3718/0 | Nov., 1996 | WO.
| |
Primary Examiner: Webman; Edward J.
Attorney, Agent or Firm: Silverman; Richard P.
Claims
What is claimed is:
1. An acidic cosmetic, dermatological or pharmaceutical liquid or gel composition
which comprises an inorganic or groan ic acid and at least one copolymer obtained
by free-radical copolymerization of
A) acryloyldimethyltaurine or acryloyldimethyltaurates, and mixtures thereof,
B) optionally, one or more further olefinically unsaturated, noncationic, comonomers
which have at least one oxygen, nitrogen, sulfur or phosphorus atom and possess
a molecular weight of less than 500 g/mol,
C) optionally, one or more olefinically unsaturated, cationic comonomers which
have at least one oxygen, nitrogen, sulfur or phosphorus atom and possess a molecular
weight of less than 500 g/mol,
D) one or more silicon-containing components capable of free-radical polymerization
and having a functionality of at least one,
E) optionally, one or more fluorine-containing components capable of free-radical
polymerization and having a functionality of at least one,
F) optionally, one or more olefinically mono- or polyunsaturated, macromonomers
each possessing at least one oxygen, nitrogen, sulfur or phosphorus atom and having
a number-average molecular weight of greater then or equal to 200 g/mol, the macromonomers
not being a silicon-containing component D) or fluorine-containing component E),
and where at least one macr6monomer is a macromonomer of formula (IV)
##STR5##
in which
R
3, R
4, R
5, and R
6 independently
of one another are hydrogen or n-aliphatic, iso-aliphatic. olefinic, cycloaliphatic,
arylaliphatic or aromatic (C
1-C
30) hydrocarbon radicals,
v and w independently of one another are from 0 to 500, the sum of v and w is
on average≧1, and Y is selected from the group consisting of —O—,
—C(O)—, —C(O)—O—, —S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2O—, —O—SO
2—O—,
—O—SO
2—O—, —O—SO—O—,
—PH—, —P(CH
3)—, —PO
3—,
—NH—, and —N(CH
3)—,
G) optionally, the copolymerization taking place in the presence of at least
one polymeric additive having number-average molecular weights of from 200 g/mol
to 10
9 g/mol,
H) with the proviso that component A) is copolymerized with at least one component
selected from one of the components D) to G), and wherein said acid ranges from
0.05 to 20 weight percent of said composition.
2. The acidic composition as claimed in claim 1, wherein the comonomers B) are
selected from the group consisting of unsaturated carboxylic acids, salts of unsaturated
carboxylic acids, anhydrides of unsaturated carboxylic acids, esters of unsaturated
carboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic
alcohols having 1 to 22 carbon atoms, open-chain N-vinyl amides, cyclic N-vinyl
amides having a ring size of from 3 to 9, amides of acrylic acid, amides of methacrylic
acid, amides of substituted acrylic acids, amides of substituted methacrylic acids,
2-vinylpyridine, 4-vinylpyridine, vinyl acetate; styrene, acrylonitrile, vinyl
chloride, vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or the
esters or salts thereof, vinylsulfonic acid or the esters or salts thereof, allylphosphonic
acid or the esters or salts thereof, methallylsulfonic acid or the esters or salts
thereof, and mixtures thereof.
3. The acidic composition as claimed in claim 1, wherein the comonomers C) are
selected from the group consisting of diallyldimethylammonium chloride (DADMAC),
[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC),
[2-(acryloyloxy)ethyl]trimethylammonium chloride,
[2-methacrylamidoethyl]trimethylammonium chloride,
[2-(acrylamido)ethyl]trimethylammonium chloride,
N-methyl-2-vinylpyridinium chloride,
N-methyl-4-vinylpyridinium chloride,
dimethylaminoethyl methacrylate,
dimethylaminopropylmethacrylamide,
methacryloylethyl N-oxide,
methacryloylethylbetaine, and mixtures thereof.
4. The acidic composition as claimed claim 1, wherein said silicon-containing
components D) are compounds of the formula (I)
R
1-Z-[(Si(R
3R
4)—O—)
w—(Si(R
5R
6)—O)
x—]—R
2 (I)
where
R
1 represents a polymerizable function from a vinylically unsaturated compound;
Z is a chemical bridge,
R
3, R
4, R
5, and R
6 independently
of one another are —CH
3, —O—CH
3, —C
6H
5
or —O—C
6H
5;
w and x denote numbers from 0 to 500, it being necessary for either w or x to
be greater than zero; and
R
2 is a saturated or unsaturated aliphatic, cycloaliphatic, arylaliphatic
or aromatic radical having in each case 1 to 50 carbon atoms or a group of the
formulae —OH, —NH
2, —N(CH
3)
2,
—R
7 or a group -Z-R
1, where Z and R
1 have
the meanings mentioned above, R
1 and
R
7 is selected from the group consisting of the formula —O—Si(CH
3)
3,
—O—Si(phenyl)
3, —O—Si(O—Si(CH
3)
3)
3)
2CH
3)
and —O—Si(O—Si(phenyl)
3)
2phenyl).
5. The acidic composition of claim 1, wherein the fluorine-containing components
E) are compounds of the formula (II)
R
1—Y—C
rH
2rC
sF
2sCF
3 (II)
where
R
1 is a polymerizable function from vinylically unsaturated compounds;
Y is a chemical bridge, and
r, s are stoichiometric coefficients which independently of one another denote
numbers from 0 to 200.
6. The acidic composition of claim 1, wherein component F) further comprises
one or more of the formula (III)
R
1—Y—[(A)
v-(B)
w-(C)
x-(D)
z]—R
2 (III)
where R
1 represents a polymerizable function from a vinylically unsaturated compound;
Y is a chemical bridge,
A, B, C, and D independently of one another are discrete chemical repeating units;
v, w, x, and z independently of one another amount to from 0 to 500, the sum
of v, w, x, and z being on average ≧1; and
R
2 is a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic
or aromatic (C
1-C
50) hydrocarbon radical, OH, —NH
2
or —N(CH
3)
2 or is [—Y—R
1].
7. The acidic composition of claim 1, wherein the polymeric additive G) is selected
from the group consisting of a polyalkylene glycol, an alkylpolyglycol and mixtures
thereof or a homopolymer or copolymer of a compound selected from the group consisting
of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide. propylene
oxide, acryloyldimethyltaurine, N-vinylcaprolactone, N-vinylmethylacetamide, acrylamide,
acrylic acid, methacrylic acid, N-vinylmorpholide, hydroxymethyl methacrylate,
diallyldimethylammonium chloride (DADMAC), [2-(methacryloyloxy)ethyl]trimethylammonium
chloride (MAPTAC), and mixtures thereof.
8. The acidic composition of claim 1, wherein the copolymerization takes place
in the presence of at least one polymeric additive G).
9. The acidic composition of claim 1, wherein the copolymer is crosslinked.
10. The acidic composition of claim 1, wherein the copolymer is prepared by precipitation
polymerization in tert-butanol.
11. The acidic composition of claim 1, wherein the copolymer is water-soluble
or water-swellable.
12. The acidic composition of claim 1, which comprises, based on the finished
composition, from 0.01 to 10% by weight of the copolymer.
13. The acidic composition of claim 1, which possesses a pH of less than or equal
to 6.5.
14. The acidic composition of claim 13, which possesses a pH in the range from
2 to 6.5.
15. An acidic cosmetic, dermatological or pharmaceutical liquid or gel composition
which comprises an inorganic or organic acid and at least one copolymer obtained
by free-radical copolymerization of
A) acryloyldimethyltaurine or acryloyldimethyltaurates, and mixtures thereof,
B) optionally, one or more further olefinically unsaturated, noncationic, comonomers
which have at least one oxygen, nitrogen, sulfur or phosphorus atom and possess
a molecular weight of less than 500 g/mol,
C) optionally, one or more olefinically unsaturated, cationic comonomers which
have at least one oxygen, nitrogen, sulfur or phosohorus atom and possess a molecular
weight of less than 500 g/mol,
D) one or more silicon-containing components capable of free-radical polymerization
and having a functionality of at least one,
E) optionally, one or more fluorine-containing components capable of free-radical
polymerization and having a functionality of at least one,
F) optionally, one or more olefinically mono- or polyunsaturated, macromonomers
each possessing at least one oxygen, nitrogen, sulfur or phosphorus atom and having
a number-average molecular weight of greater than or equal to 200 g/mol, the macromonomers
not being a silicon-containing component D) or fluorine-containing component E),
and where at least one macromonomer is a macromonomer of formula (IV)
##STR6##
in which
R
3, R
4, R
5, and R
6 independently
of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic,
arylaliphatic or aromatic (C
1-C
30) hydrocarbon radicals,
v and w independently of one another are from 0 to 500, the sum of v and w is
on average ≧1, and Y is selected from the group consisting of —O—,
—C(O)—, —C(O)—O—, —S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2O—, —O—SO
2—O—,
—O—SO
2—O—SO—O—, —PH—,
—P(CH
3)—, —PO
3—, —NH—,
and —N(CH
3)—,
G) optionally, the copolymerization taking place in the presence of at least
one polymeric additive having number-average molecular weights of from 200 g/mol
to 10
9 g/mol,
H) with the proviso that component A) is copolymerized with at least one component
selected from one of the components D) to G), and wherein said acid ranges from
0.05 to 20 weight percent of said composition
wherein said acid is i) an alpha-hydroxy acid or ii) an acid selected from the
group consisting of glycolic acid, lactic acid, citric acid, tartaric acid, mandelic
acid, salicylic acid, ascorbic acid, pyruvic acid, oligooxa-monocarboxylic and
-dicarboxylic acids, fumaric acid, retinoic acid, aliphatic and organic sulfonic
acid, benzoic acid, kojic acid, fruit acid, malic acid, gluconic acid, galacturonic
acid, and mixtures thereof, or iii) a compound selected from the group consisting
of an acidic plant extract, a fruit extract, a fruit extract derivative, an acid
plant extract derivative, and mixtures thereof, or a mixture of i), ii) and iii).
16. The acidic composition of claim 1, which is in the form of an emulsion, aqueous
gel or surfactant-containing formulation.
17. The acidic composition of claim 1, which is in the form of a rinse-off composition.
18. The acidic composition of claim 1, which is in the form of a leave-on composition.
19. The acidic composition of claim 4 wherein the chemical bridge Z is selected
from the group consisting of —O—, —((C
1-C
50)alkylene)-,
—((C
6-C
30)arylene)-, —((C
5-C
8)cycloalkylene)-,
—((C
1-C
50)alkenylene)-, -(polypropylene oxide)
n-,
-(polyethylene oxide)
o-, -(polypropylene oxide)
n(polyethylene
oxide)
o-, and mixtures thereof, where n and a independently of one another
denote numbers from 0 to 200 and the distribution of EO/PO units can be random
or in block form, and/or selected from the group consisting of —((C
1-C
10)alkyl)-(Si(OCH
3)
2)—and —(Si(OCH
3)
2)—.
20. The acidic composition of claim 4 wherein, R
1 is a radical selected
from the group consisting of vinyl, allyl, methallyl, methylvinyl, acryloyl methacryloyl,
crotonyl, senecionyl, itaconyl, maleyl, fumaryl, styryl, and mixtures thereof.
21. The acidic composition of claim 5 wherein, R
1 is a radical selected
from the group consisting of vinyl, allyl, methallyl, methylvinyl, acryloyl, methacryloyl,
crotonyl, senecionyl, itaconyl, maleyl, fumaryl, styryl, and mixtures thereof.
22. The acidic composition of claim 6 wherein, R
1 is a radical selected
from the group consisting of vinyl, allyl, methallyl, methylvinyl, acryloyl, methacryloyl,
crotonyl, senecionyl, itaconyl, maleyl, fumaryl, styryl, and mixtures thereof.
23. The acidic composition of claim 5, wherein the chemical bridge Y is selected
from the group consisting of —O—, —C(O)—, —C(O)—O—,
—S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2—O—,
—O—SO
2—O—, —O—S(O)—O—,
—PH—, —P(CH
3)—, —PO
3—,
—NH—, —N(CH
3)—, —O—(C
1-C
50)alkyl-O—,
—O -phenyl-O—, —O-benzyl-O—, —O—(C
5-C
8)cycloalkyl-O—,
—O—(C
1-C
50)alkenyl-O—, —O—(CH(CH
3)—CH
2—O)
n—,
—O—(CH
2—CH
2O)
n—, —O—([CH—CH
2—O]
n—[CH
2—CH
2—O]
m)
o—,
where n, m, and o independently of one another denote numbers from 0 to 200, and
mixtures thereof.
24. The acidic composition of claim 6, wherein Y is a bridging group selected
from the group consisting of —O—, —S—, —C(O)—,
—C(O)—O—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2O—, —O—SO
2—O—,
—O—SO—O—, —PH—, —P(CH
3)—,
—PO
3—, —NH—, —N(CH
3)—,
and mixtures thereof.
25. The acidic composition of claim 6 wherein the discrete repeating units of
A, B, C, and D are originating from a unit selected from the group consisting of
acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid,
methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate,
styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide, diisopropylacrylamide,
and mixtures thereof.
26. The acidic composition of claim 6 wherein the discrete repeating units of
A, B, C, and D are originating from a unit of ethylene oxide or propylene oxide.
27. The acidic composition of claim 6, wherein v, w, x, and z independently of
one another amount to from 1 to 30.
28. The acidic composition of claim 15, which contains from 0.5 to 10% by weight
of said acid.
29. A liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
which comprises from 0.05 to 20 weight percent of an organic or inorganic acid
end at least one copolymer obtained by free-radical copolymerization of acryloyldimethyltaurine
or acryloyldimethyltaurates, or mixtures thereof, with at least one component selected
from the group consisting of:
a) one or more silicon-containing component (D) capable of free-radical polymerization
and having a functionality of at least one,
b) one or more fluorine-containing component (E) capable of free-radical polymerization
and having a functionality of at least one,
c) one or more olefinically mono- or polyunsaturated, macromonomer (F) (each
possessing at least one oxygen, nitrogen, sulfur or phosphorus atom and having
a number-average molecular weight of greater than or equal to 200 g/mol, the macromonomer
not being the silicon-containing component a) or the fluorine-containing component
b), and where at least one macromonomer is a macromonomer of formula (IV)
##STR7##
in which
R
3, R
4, R
5, and R
8 independently
of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic,
arylaliphatic or aromatic (C
1-C
30) hydrocarbon radicals,
v and w independently of one another are from 0 to 500, the sum of v and w is
on average ≧1, and Y is selected from the group consisting of —O—,
—C(O)—, —C(O)—O—, —S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2O—, —O—SO
2—O—,
—O—SO—O—, —PH—, —P(CH
3)—,
—PO
3—, —NH—, and —N(CH
3)—, and
d) at least one polymeric additive (G) having number-average molecular weights
of from 200 g/mol to 10
9 g/mol,
e) one or more further olefinically unsaturated, noncationic comonomer (B) which
have at least one oxygen, nitrogen, sulfur or phosphorous atom and possess a molecular
weight of less than 500 g/mol,
f) one or more olefinically unsaturated, cationic comonomer (C) which has at
least one oxygen, nitrogen, sulfur or phosphorus atom and possess a molecular weight
of less than 500 g/mol,
with the proviso that when component B or C is copolymerized, at least one further
component is selected from the group consisting of components D, E, F, and G.
30. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 29, wherein said macromonomer c) is crosslinking.
31. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 29, wherein said olefinically unsaturated, noncationic comonomer e) is crosslinking.
32. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 29, wherein the at least one copolymer is obtained by the free-radical
polymerization of acryloyldimethyltaurine or acryloyldimethyltaurates, or mixtures
thereof (A) and the at least one component is selected from the group consisting
of component (F); component (D); component (E); components (C) and (D); components
(C) and (E); and components (D) and (F).
33. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 32, wherein the at least one copolymer is obtained by the free-radical
polymerization in the absence of (G).
34. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 32, wherein the at least one copolymer is obtained by the free-radical
polymerization in the presence of (G).
35. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 29, wherein said composition comprises from 0.5 to 20 weight percent of
the organic or inorganic acid.
36. The liquid or gel acidic cosmetic, dermatological or pharmaceutical composition
of claim 29, wherein the organic acid is i) an alpha-hydroxy acid or ii) an acid
selected from the group consisting of glycolic acid, lactic acid, citric acid,
tartaric acid, mandelic acid, salicylic acid, ascorbic acid, pyruvic acid, oligooxa-monocarboxylic
and -dicarboxylic acids, fumaric acid, retinoic acid, aliphatic and organic sulfonic
acid, benzoic acid, kojic acid, fruit acid, malic acid, gluconic acid, galacturonic
acid, and mixtures thereof, or iii) a compound selected from the group consisting
of an acidic plant extract, a fruit extract, a fruit extract derivative, an acid
plant extract derivative, and mixtures thereof or a mixture of i), ii) and iii).
Description
The present invention relates to acidic cosmetic, pharmaceutical, and dermatological
compositions comprising comb copolymers based on acryloyldimethyltaurine.
The cosmetic, pharmaceutical, and dermatological compositions in use at the present
time mostly take the form of oil-in-water emulsions, i.e., systems composed of
a continuous aqueous phase and a discontinuous, dispersed oil phase, or of water-in-oil
emulsions, i.e., systems composed of a continuous, fat-containing phase and a discontinuous,
dispersed aqueous phase. The water-in-oil emulsions therefore include a continuous
oil phase and allow a fatty film to form at the skin surface that prevents transepidermal
water loss and protects the skin against external aggressions. These emulsions
are particularly suitable for protecting and enriching the skin and, in particular,
for treating dry skin. The oil-in-water emulsions, for their part, impart to the
skin upon application a soft, less greasy and more gentle feel than the water-in-oil emulsions.
Starting a number of years ago, the use of alpha-hydroxy acids (AHAs) in
cosmetic, pharmaceutical, and dermatological compositions has become established.
Particularly in the case of anti-aging products the aim is for desquamation and
renewal of the topmost layers of skin of the Stratum Corneum. AHAs are used for
this gentle peeling. Examples of representatives of the AHAs are glycolic acid
from sugar cane, lactic acid from curdled milk, citric acid from citrus fruits,
tartaric acid from wine, salicylic acid, and pyruvic acid from papaya fruits.
The use of AHAs and their salts makes it necessary in some cases to adjust the
pH of the cosmetic or dermatological compositions to a distinctly acidic range.
Since the cosmetic sector uses polyelectrolytes based on (meth)acrylic acid,
preferably as thickeners and gel formers, the desired low pH causes very great
difficulties in ensuring that the end formulations are of adequate stability. A
substantial disadvantage of the thickeners based on poly(meth)acrylic acid is the
heavy pH dependence of the thickening effect. Thus, generally speaking, adequate
viscosity is only developed when the pH of the formulation is adjusted to more
than 6 so that the poly(meth)acrylic acid is in neutralized form.
Over the course of recent years, polymers have become established on the market
which have allowed the formulation of low-surfactant emulsions and even surfactant-free
pseudo emulsions (WO 96/37180 and U.S. Pat. No. 5,736,125). By hydrophobic modification
of conventional poly(meth)acrylates, an access route has been found here to polymers
which may have both thickening and emulsifying/dispersing properties. Examples
of commercial hydrophobically modified poly(meth)acrylates are ®Pemulen TR-1
and TR-2 from BF Goodrich and ®ACULYN 22 from Rohm & Haas. Since, however,
these hydrophobically modified polymers are without exception constructed on the
basis of (meth)acrylic acid, they also possess the abovementioned disadvantages
of the poly(meth)acrylates and therefore in particular are not of unrestricted
suitability for the formulation of acidic cosmetic, pharmaceutical, and dermatological preparations.
There is therefore a need for acidic cosmetic, dermatological, and pharmaceutical
compositions which are easy to prepare and possess outstanding rheological and
sensorial properties and high stability.
Surprisingly it has now been found that a new class of copolymers based
on acryloyldimethyltaurine (AMPS)—and suitable in the capacity of a thickener,
bodying agent, emulsifier, dispersant and/or stabilizer—are outstandingly
suitable for the formulation of acidic cosmetic, pharmaceutical, and dermatological preparations.
The invention accordingly provides acidic cosmetic, dermatological, and pharmaceutical
compositions comprising at least one copolymer obtainable by free-radical copolymerization of
A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,
B) if desired, one or more further olefinically unsaturated, noncationic,
optionally crosslinking, comonomers which have at least one oxygen, nitrogen, sulfur
or phosphorus atom and possess a molecular weight of less than 500 g/mol,
C) if desired, one or more olefinically unsaturated, cationic comonomers
which have at least one oxygen, nitrogen, sulfur or phosphorus atom and possess
a molecular weight of less than 500 g/mol,
D) if desired, one or more silicon-containing components capable of free-radical
polymerization and having a functionality of at least one,
E) if desired, one or more fluorine-containing components capable of free-radical
polymerization and having a functionality of at least one,
F) if desired, one or more olefinically mono- or polyunsaturated, optionally
crosslinking macromonomers each possessing at least one oxygen, nitrogen, sulfur
or phosphorus atom and having a number-average molecular weight of greater than
or equal to 200 g/mol, the macromonomers not being a silicon-containing component
D) or fluorine-containing component E),
G) the copolymerization taking place if desired in the presence of at least
one polymeric additive having number-average molecular weights of from 200 g/mol
to 109 g/mol,
H) with the proviso that component A) is copolymerized with at least one
component selected from one of the groups D) to G).
The copolymers of the invention preferably possess a molecular weight of from
10
3 g/mol to 10
9 g/mol, more preferably from 10
4 to
10
7 g/mol, with particular preference from 5*10
4 to 5*10
6 g/mol.
The acryloyldimethyltaurates can be the organic or inorganic salts of acryloyldimethyltaurine
(acrylamidopropyl-2-methyl-2-sulfonic acid). Preference is given to the Li
+,
Na
+, K
+, Mg
++, Ca
++, Al
+++
and/or NH
4+ salts. Likewise preferred are the monoalkylammonium,
dialkylammonium, trialkylammonium and/or tetraalkylammonium salts, in which the
alkyl substituents of the amines may independently of one another be (C
1-C
22)-alkyl
radicals or (C
2-C
10)-hydroxyalkyl radicals. Preference is
also given to mono- to triethoxylated ammonium compounds with different degrees
of ethoxylation. It should be noted that mixtures of two or more of the abovementioned
representatives are also embraced by the invention.
The degree of neutralization of the acryloyldimethyltaurine can be between 0
and 100%, with particular preference being given to a degree of neutralization
of more than 80%.
Based on the total mass of the copolymers, the amount of acryloyldimethyltaurine
and/or acryloyldimethyltaurates is at least 0.1% by weight, preferably from 20
to 99.5% by weight, more preferably from 50 to 98% by weight.
As comonomers B) it is possible to use all olefinically unsaturated noncationic
monomers whose reaction parameters allow copolymerization with acryloyldimethyltaurine
and/or acryloyldimethyltaurates in the respective reaction media. Preferred comonomers
B) are unsaturated carboxylic acids and their anhydrides and salts, and also their
esters with aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic alcohols
having a carbon number of from 1 to 30.
Particularly preferred unsaturated carboxylic acids are acrylic acid,
methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid,
itaconic acid, and senecic acid.
Preferred counterions are Li
+, Na
+, K
+,
Mg
++, Ca
++, Al
+++, NH
4+,
monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium
radicals, in which the alkyl substituents of the amines independently of one another
can be (C
1-C
22)-alkyl radicals or (C
2-C
10)-hydroxyalkyl
radicals. It is additionally possible to employ mono- to triethoxylated ammonium
compounds with a different degree of ethoxylation. The degree of neutralization
of the carboxylic acids can be between 0 and 100%.
Further preferred comonomers B) are open-chain N-vinyl amides, preferably
N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA)
and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams) with a ring size
of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; amides of
acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N,N-dimethyl-acrylamide,
N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylated acrylamides and
methacrylamides, preferably hydroxyethyl methacrylate, hydroxy-methylmethacrylamide,
hydroxyethylmethacrylamide, hydroxypropylmethacrylamide, and mono [2-(methacryloyloxy)ethyl]
succinate; N,N-dimethylamino methacrylate; diethylaminomethyl methacrylate; acrylamido-
and methacrylamido-glycolic acid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl
methacrylate; styrene; acrylonitrile; vinyl chloride; stearyl acrylate; lauryl
methacrylate; vinylidene chloride; and/or tetrafluoroethylene.
Likewise suitable comonomers B) are inorganic acids and their salts and
esters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid, allylphosphonic
acid, and methallylsulfonic acid.
The weight fraction of the comonomers B), based on the total mass of the copolymers,
can be from 0 to 99.8% by weight and is preferably from 0.5 to 80% by weight, more
preferably from 2 to 50% by weight.
Suitable comonomers C) include all olefinically unsaturated monomers with
cationic charge which are capable of forming copolymers with acryloyldimethyltaurine
or its salts in the chosen reaction media. The resulting distribution of the cationic
charges across the chains can be random, alternating, blocklike or gradientlike.
It may be noted that the cationic comonomers C) also comprehend those which bear
the cationic charge in the form of a betaine, zwitterionic or amphoteric structure.
Comonomers C) for the purposes of the invention are also amino-functionalized precursors
which can be converted by polymer-analogous reactions into their corresponding
quaternary derivatives (e.g., reaction with dimethyl sulfate, methyl chloride),
zwitterionic derivatives (e.g., reaction with hydrogen peroxide), betaine derivatives
(e.g., reaction with chloroacetic acid), or amphoteric derivatives.
Particularly preferred comonomers C) are
diallyldimethylammonium chloride (DADMAC),
[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC),
[2-(acryloyloxy)ethyl]trimethylammonium chloride,
[2-methacrylamidoethyl]trimethylammonium chloride,
[2-(acrylamido)ethyl]trimethylammonium chloride,
N-methyl-2-vinylpyridinium chloride,
N-methyl-4-vinylpyridinium chloride,
dimethylaminoethyl methacrylate,
dimethylaminopropylmethacrylamide,
methacryloylethyl N-oxide and/or
methacryloylethyl betaine.
The weight fraction of the comonomers C), based on the total mass of the copolymers,
can be from 0.1 to 99.8% by weight, more preferably from 0.5 to 30% by weight,
and very preferably from 1 to 20% by weight.
Suitable polymerizable silicon-containing components D) are all compounds
which are olefinically at least monounsaturated and capable of free-radical copolymerization
under the reaction conditions chosen in each case. The distribution of the individual
silicone-containing monomers across the polymer chains which form need not necessarily
be random. The invention also embraces the formation, for example, of blocklike
(including multiblock) or gradientlike structures. Combinations of two or more
different silicone-containing representatives are also possible. The use of silicone-containing
components having two or more polymerization-active groups leads to the construction
of branched or crosslinked structures.
Preferred silicone-containing components D) are those of formula (I).
R
1-Z-[(Si(R
3R
4)—O—)
w—(Si(R
5R
6)—O)
x—]—R
2 (I)
In this formula R
1 represents a polymerizable function from the group
of the vinylically unsaturated compounds which is suitable for the synthesis of
polymeric structures by a free-radical route. R
1 represents preferably
a vinyl, ally, methallyl, methylvinyl, acryloyl (CH
2═CH—CO—),
methacryloyl (CH
2═C[CH
3]—CO—), crotonyl,
senecionyl, itaconyl, maleyl, fumaryl or styryl radical.
The attachment of the silicone-containing polymer chain to the reactive end group
R
1 requires a suitable chemical bridge Z. Preferred bridges Z are —O—,
((C
1-C
50)alkylene), —((C
6-C
30)arylene)-,
—((C
5-C
8)cycloalkylene)-, —((C
1-C
50)alkenylene)-,
-(polypropylene oxide)
n-, -(polyethylene oxide)
o-, -(polypropylene-oxide)
n(polyethylene
oxide)
o-, where n and o independently of one another denote numbers
from 0 to 200 and the distribution of the EO/PO units can be random or in the form
of blocks. Further suitable bridge groups Z are —((C
1-C
10)alkyl)-(Si(OCH
3)
2)—
and —(Si(OCH
3)
2)—.
The polymeric central moiety is represented by silicone-containing repeating
units. The radicals R
3, R
4, R
5, and R
6 denote
independently of one another —CH
3, —O—CH
3,
—C
6H
5 or —O—C
6H
5.
The indices w and x represent stoichiometric coefficients which amount independently
of one another to from 0 to 500, preferably 10 to 250.
The distribution of the repeating units across the chain can be not only purely
random but also blocklike, alternating or gradientlike.
R
2 stands for an aliphatic, olefinic, cycloaliphatic, arylaliphatic
or aromatic (C
1-C
50) hydrocarbon radical (linear or branched)
or —OH, —NH
2, —N(CH
3)
2, —R
7
or for the structural unit [-Z-R
1]. The definition of the two
variables Z and R
1 has already been explained. R
7 stands
for further Si-containing groups. Preferred radicals R
7 are —O—Si(CH
3)
3,
—O—Si(Ph)
3, —O—Si(O—Si(CH
3)
3)
2CH
3)
and —O—Si(O—Si(Ph)
3)
2Ph. If R
2 is
an element of the group [-Z-R
1] the monomers in question are difunctional
monomers which can be used to crosslink the polymer structures which form. Formula
(I) describes not only silicone-containing polymer species with vinylic functionalization
and a polymer-typical distribution, but also defined compounds having discrete
molecular weights.
Particularly preferred silicone-containing components are the following
components with acrylic or methacrylic modification:
##STR1##
methacryloyloxypropylmethylsilyl-endblocked polydimethylsiloxanes (f=2 to 500)
##STR2##
methacryloyloxypropyl-endblocked polydimethylsiloxanes (f=2 to 500)
##STR3##
vinyldimethoxysilyl-endblocked polydimethylsiloxanes (f=2-500).
Based on the total mass of the copolymers, suitable silicon-containing components
can be present in an amount of up to 99.9% by weight, preferably from 0.5 to 30%
by weight, more preferably from 1 to 20% by weight.
Suitable polymerizable fluorine-containing components E) include all compounds
which are olefinically at least monounsaturated and which are capable of free-radical
copolymerization under the reaction conditions chosen in each case. The distribution
of the individual fluorine-containing monomers across the polymer chains which
form need not necessarily be random. The invention also embraces the formation
of blocklike (including multiblock) or gradientlike structures, for example. Combinations
of two or more different fluorine-containing components E) are also possible, it
being clear to the expert that monofunctional representatives lead to the formation
of comb-shaped structures while di-, tri-, or polyfunctional components E) lead
to structures which are at least partly crosslinked.
Preferred fluorine-containing components E) are those of formula (II).
R
1—Y—C
rH
2rC
sF
2sCF
3 (II)
In this formula R
1 represents a polymerizable function from the group
of the vinylically unsaturated compounds which is suitable for the construction
of polymeric structures by a free-radical route. R
1 is preferably a
vinyl, allyl, methallyl, methylvinyl, acryloyl (CH
2═CH—CO—),
methacryloyl (CH
2═C[CH
3]—CO—), crotonyl,
senecionyl, itaconyl, maleyl, fumaryl or styryl radical, more preferably an acryloyl
or methacryloyl radical.
The attachment of the fluorine-containing group to the reactive end group R
1
requires a suitable chemical bridge Y. Preferred bridges Y are —O—,
—C(O)—, —C(O)—O—, —S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2—O—,
—O—SO
2—O—, —O—S(O)—O—,
—PH—, —P(CH
3)—, —PO
3—,
—NH—, —N(CH
3)—, —O—(C
1-C
50)alkyl-O—,
—O-phenyl-O—, —O-benzyl-O—, —O—(C
5-C
8)cycloalkyl-O—,
—O—(C
1-C
50)alkenyl-O—, —O—(CH(CH
3)—CH
2—O)
n—,
—O—(CH
2—CH
2—O)
n—,
and —O—([CH—CH
2—O]
n—[CH
2—CH
2—O]
m)
o—,
where n, m, and o independently of one another denote numbers from 0 to 200 and
the distribution of the EO and PO units can be random or in the form of blocks.
r and s are stoichiometric coefficients which independently of one another denote
numbers from 0 to 200.
Preferred fluorine-containing components E) of formula (II) are
perfluorohexylethanol methacrylate,
perfluorohexoylpropanol methacrylate,
perfluoroctylethanol methacrylate,
perfluoroctylpropanol methacrylate,
perfluorohexylethanolyl polyglycol ether methacrylate,
perfluorohexoylpropanolyl poly[ethylglycol-co-propylene glycol ether] acrylate,
perfluoroctylethanolyl poly[ethylglycol-block-co-propylene glycol ether] methacrylate,
perfluoroctylpropanolyl polypropylene glycol ether methacrylate.
Based on the total mass of the copolymers the amount of suitable fluorine-containing
components can be up to 99.9% by weight, preferably from 0.5 to 30% by weight,
more preferably from 1 to 20% by weight.
The macromonomers F) are at least singly olefinically functionalized polymers
having one or more discrete repeating units and a number-average molecular weight
of greater than or equal to 200 g/mol. In the copolymerization it is also possible
to use mixtures of chemically different macromonomers F). The macromonomers are
polymeric structures composed of one or more repeating units and have a molecular
weight distribution characteristic of polymers. Preferred macromonomers F) are
compounds of formula (III).
R
1—Y-[(A)
v-(B)
w—(C)
x-(D)
z]-R
2 (III)
R
1 represents a polymerizable function from the group of the vinylically
unsaturated compounds which are suitable for constructing polymeric structures
by a free-radical route. Preferably R
1 is a vinyl, allyl, methallyl,
methylvinyl, acryloyl (CH
2═CH—CO—), methacryloyl
(CH
2═([CH
3]—CO—), crotonyl, senecionyl,
itaconyl, maleyl, fumaryl or styryl radical.
Attachment of the polymer chain to the reactive end group requires a suitable
bridging group Y. Preferred bridges Y are —O—, —C(O)—,
—C(O)—O—, —S—, —O—CH
2—CH(O—)—CH
2OH,
—O—CH
2—CH(OH)—CH
2O—, —O—SO
2—O—,
—O—SO
2—O—, —O—SO—O—,
—PH—, —P(CH
3)—, —PO
3—,
—NH—, and —N(CH
3)—, more preferably —O—.
The polymeric central moiety of the macromonomer is represented by the discrete
repeating units A, B, C, and D. Preferably the repeating units A, B, C, and D are
derived from: acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS,
acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid,
vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide,
and diisopropylacrylamide.
The indices v, w, x, and z in formula (III) represent the stoichiometric coefficients
relating to the repeating units A, B, C, and D. v, w, x, and z amount independently
of one another to from 0 to 500, preferably 1 to 30, it being necessary for the
sum of the four coefficients on average to be ≧1.
The distribution of the repeating units over the macromonomer chain can be random,
blocklike, alternating or gradientlike.
R
2 denotes a linear or branched aliphatic, olefinic, cycloaliphatic,
arylaliphatic or aromatic C
1-C
50 hydrocarbon radical, OH,
—NH
2, —N(CH
3)
2 or is the structural
unit [—Y—R
1].
In the case of R
2 being [—Y—R
1] the macromonomers
in question are difunctional and suitable for crosslinking the copolymers.
Particularly preferred macromonomers F) are acrylically or methacrylically
monofunctionalized alkyl ethoxylates of formula (IV).
##STR4##
R
3, R
4, R
5, and R
6 are
independently of one another hydrogen or n-aliphatic, iso-aliphatic, olefinic,
cycloaliphatic, arylaliphatic or aromatic C
1-C
30 hydrocarbon radicals.
Preferably R
3 and R
4 are H or —CH
3,
more preferably H; R
5 is H or —CH
3; and R
6 is
an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic
C
1-C
30 hydrocarbon radical.
v and w are in turn the stoichiometric coefficients relating to the ethylene
oxide
units (EO) and propylene oxide units (PO). v and w amount independently of one
another to from 0 to 500, preferably 1 to 30, it being necessary for the sum of
v and w to be on average ≧1. The distribution of the EO and PO units over
the macromonomer chain can be random, blocklike, alternating or gradientlike. Y
stands for the abovementioned bridges.
Further particularly preferred macromonomers F) have the following structure
in accordance with formula (IV):
| ®LA-030-methacry- |
H |
H |
—CH3 |
-lauryl |
3 |
0 |
| late |
| ®LA-070-methacry- |
H |
H |
—CH3 |
-lauryl |
7 |
0 |
| late |
| ®LA-200-methacry- |
H |
H |
—CH3 |
-lauryl |
20 |
0 |
| late |
| ®LA-250-methacry- |
H |
H |
—CH3 |
-lauryl |
25 |
0 |
| late |
| ®T-080-methacry- |
H |
H |
—CH3 |
-talc |
8 |
0 |
| late |
| ®T-080-acrylate |
H |
H |
H |
-talc |
8 |
0 |
| ®T-250-methacry- |
H |
H |
—CH3 |
-talc |
25 |
0 |
| late |
| ®T-250-crotonate |
—CH3 |
H |
—CH3 |
-talc |
25 |
0 |
| ®OC-030-methacry- |
H |
H |
—CH3 |
-octyl |
3 |
0 |
| late |
| ®OC-105-methacry- |
H |
H |
—CH3 |
-octyl |
10 |
5 |
| late |
| ®Behenyl-010- |
H |
H |
H |
-behenyl |
10 |
0 |
| methylaryl |
| ®Behenyl-020- |
H |
H |
H |
-behenyl |
20 |
0 |
| methylaryl |
| ®Behenyl-010- |
—CH3 |
—CH3 |
H |
-behenyl |
10 |
0 |
| senecionyl |
| ®PEG-440-diacry- |
H |
H |
H |
-acryloyl |
10 |
0 |
| late |
| ®B-11-50- |
H |
H |
—CH3 |
-butyl |
17 |
13 |
| methacrylate |
| ®MPEG-750- |
H |
H |
—CH3 |
-methyl |
18 |
0 |
| methacrylate |
| ®P-010-acrylate |
H |
H |
H |
-phenyl |
10 |
0 |
| ®O-050-acrylate |
H |
H |
H |
-oleyl |
5 |
0 |
|
Further particularly suitable macromonomers F) are esters of (meth)acrylic
acid with
(C10-C18) fatty alcohol polyglycol ethers having 8
EO units (Genapol® C-080)
C11 oxo alcohol polyglycol ethers having 8 EO units (Genapol® UD-080)
(C12-C14) fatty alcohol polyglycol ethers having 7
EO units (Genapol® LA-070)
(C12-C14) fatty alcohol polyglycol ethers having 11
EO units (Genapol® LA-110)
(C16-C18) fatty alcohol polyglycol ethers having 8
EO units (Genapol® T-080)
(C16-C18) fatty alcohol polyglycol ethers having 15
EO units (Genapol® T-150)
(C16-C18) fatty alcohol polyglycol ethers having 11
EO units (Genapol® T-110)
(C16-C18) fatty alcohol polyglycol ethers having 20
EO units (Genapol® T-200)
(C16-C18) fatty alcohol polyglycol ethers having 25
EO units (Genapol® T-250)
(C18-C22) fatty alcohol polyglycol ethers having 25
EO units and/or
iso-(C16-C18) fatty alcohol polyglycol ethers having
25 EO units.
The Genapol® grades are products of Clariant GmbH.
The molecular weight of the macromonomers F) is preferably from 200 g/mol to
10
6 g/mol, more preferably from 150 to 10
4 g/mol, and very
preferably from 200 to 5 000 g/mol.
Based on the total mass of the copolymers it is possible for the amount of
macromonomers to be up to 99.9% by weight, preferably from 0.5 to 30% by weight
or from 70 to 99.5% by weight. Particularly preferred are amounts of from 1 to
20% by weight or from 75 to 95% by weight.
Preferred copolymers are those obtainable by copolymerizing at least components
A) and F).
Further preferred copolymers are those obtainable by copolymerizing at least
components A) and D).
Further preferred copolymers are those obtainable by copolymerizing at least
components A) and E).
Further preferred copolymers are those obtainable by copolymerizing at least
components A), C) and D).
Further preferred copolymers are those obtainable by coppolymerizing at least
components A), C) and E).
Further preferred copolymers are those obtainable by copolymerizing at least
components A), D) and F).
In one preferred embodiment the copolymerization is conducted in the presence
of at least one polymeric additive G), the additive G) being added wholly or partly
in solution to the polymerization medium before the actual copolymerization. The
use of two or more additives G) is likewise in accordance with the invention. Crosslinked
additives G) may likewise be used.
The additives G) or mixtures thereof must only be wholly or partly soluble in
the chosen polymerization medium. During the actual polymerization step the additive
G) has a number of functions. On the one hand it prevents the formation of overcrosslinked
polymer fractions in the copolymer which forms in the actual polymerization step,
and on the other hand the additive G) is statistically attacked by active free
radicals in accordance with the very well-known mechanism of graft copolymerization.
Depending on the particular additive G), this results in greater or lesser fractions
of the additive being incorporated into the copolymers. Moreover, suitable additives
G) possess the property of altering the solution parameters of the copolymers which
form during the free-radical polymerization reaction in such a way that the average
molecular weights are shifted to higher values. As compared with analogous copolymers
prepared without the addition of the additives G), those prepared with the addition
of additives G) advantageously exhibit a significantly higher viscosity in aqueous solution.
Preferred additives G) are homopolymers and copolymers which are soluble
in water and/or alcohols, preferably in t-butanol. The term "copolymers" also comprehends
those having more than two different monomer types. Particularly preferred additives
G) are homopolymers and copolymers of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone,
ethylene oxide, propylene oxide, acryloyldimethyltaurine, N-vinylcaprolactam, N-vinylmethylacetamide,
acrylamide, acrylic acid, methacrylic acid, N-vinylmorpholide, hydroxyethyl methacrylate,
diallyldimethylammonium chloride (DADMAC) and/or [2-(methacryloyloxy)ethyl]trimethylammonium
chloride (MAPTAC); polyalkylene glycols and/or alkylpolyglycols.
Particularly preferred additives G) are polyvinylpyrrolidones (e.g.,
Luviskol K15®, K20® and K30® from BASF), poly(N-vinylformamides),
poly(N-vinylcaprolactams), and copolymers of N-vinylpyrrolidone, N-vinylformamide
and/or acrylic acid, which may also have been partly or fully hydrolyzed.
The molecular weight of the additives G) is preferably from 10
2 to
10
7 g/mol, more preferably from 0.5*10
4 to 10
6 g/mol.
The amount in which the polymeric additive G) is used, based on the total mass
of the monomers to be polymerized during the copolymerization, is preferably from
0.1 to 90% by weight, more preferably from 1 to 20% by weight, and with particular
preference from 1.5 to 10% by weight.
In another preferred embodiment the copolymers of the invention are crosslinked,
i.e., they contain comonomers having at least two polymerizable vinyl groups. Preferred
crosslinkers are methylenebisacrylamide; methylenebismethacrylamide; esters of
unsaturated monocarboxylic and polycarboxylic acids with polyols, preferably diacrylates
and triacrylates, dimethacrylates and trimethacrylates, more preferably butanediol
and ethylene glycol diacrylate and methacrylate, trimethylolpropane triacrylate
(TMPTA) and trimethylol
