U.S. patent application number 11/900510 was filed with the patent office on 2008-02-28 for tenside composition containing gemini tensides and co-amphiphiles and production and use thereof.
Invention is credited to Gerd H. Dahms, Klaus Kwetkat.
Application Number | 20080051472 11/900510 |
Document ID | / |
Family ID | 7921748 |
Filed Date | 2008-02-28 |
United States Patent
Application |
20080051472 |
Kind Code |
A1 |
Kwetkat; Klaus ; et
al. |
February 28, 2008 |
Tenside composition containing gemini tensides and co-amphiphiles
and production and use thereof
Abstract
The subject invention relates to surfactant compositions of
gemini surfactants and co-amphiphile(s), to a process for preparing
such compositions, and to their uses, especially as emulsifiers and
dispersants.
Inventors: |
Kwetkat; Klaus; (Bergkamen,
DE) ; Dahms; Gerd H.; (Duisburg, DE) |
Correspondence
Address: |
C. James Bushman;Browning Bushman
Suite 1800
5718 Westheimer
Houston
TX
77057-5771
US
|
Family ID: |
7921748 |
Appl. No.: |
11/900510 |
Filed: |
September 12, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10798164 |
Mar 10, 2004 |
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11900510 |
Sep 12, 2007 |
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09831796 |
Aug 13, 2001 |
6710022 |
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10798164 |
Mar 10, 2004 |
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Current U.S.
Class: |
516/27 ;
252/182.12; 252/182.3; 516/31 |
Current CPC
Class: |
A61Q 5/00 20130101; A61K
8/342 20130101; A61K 8/44 20130101; A61Q 19/00 20130101; A61K 8/466
20130101; C01G 23/047 20130101; A61K 8/602 20130101; A61K 2800/54
20130101; A61Q 5/02 20130101; C11D 1/528 20130101; A61K 8/362
20130101; B01F 17/0042 20130101; A61K 8/85 20130101; A61K 8/06
20130101; C01G 9/02 20130101; A61K 8/29 20130101; A61K 2800/596
20130101; C09C 1/3669 20130101; A61K 8/375 20130101; A61K 8/42
20130101; C09C 1/043 20130101; A61K 8/86 20130101; A61K 8/41
20130101; B01F 17/0085 20130101; A61K 8/04 20130101; A61K 8/27
20130101; A61Q 19/10 20130101; A61K 8/345 20130101 |
Class at
Publication: |
516/027 ;
252/182.12; 252/182.3; 516/031 |
International
Class: |
B01F 3/08 20060101
B01F003/08; B01F 3/12 20060101 B01F003/12; C09K 3/00 20060101
C09K003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 13, 1999 |
DE |
19943668.1 |
Claims
1. (canceled)
2. The surfactant composition of claim 49, characterized in that
the surfactant composition comprises (A) 5 to 60 wt %, referring to
components (A) and (B), of said gemini surfactant.
3. The surfactant composition according to claim 49, further
comprising (C) at least 0.1 wt % water, referring to the total
composition.
4. A surfactant composition according to claim 49, further
comprising (D) at least 0.1 wt % of one or more oil component(s),
referring to the total composition.
5. A surfactant composition according to claim 49, wherein the
co-amphiphile is selected from the group consisting of a C.sub.6-
to C.sub.40-alcohol, a C.sub.6- to C.sub.24-carboxylic acid, a
sorbitan(C.sub.6- to C.sub.22-)ester, a methylglucoside(C.sub.6- to
C.sub.22-)ester, a sugar(C.sub.6- to C.sub.22-)ester, a mono-, di-,
or triglyceride of a C.sub.6- to C.sub.22-carboxylic acid, a lactic
acid- or citric acid-esterified derivative of the mono- or
diglycerides of a C.sub.6- to C.sub.22-carboxylic acid, a
polyglycerol(C.sub.6- to C.sub.22-)ester, a
propyleneglycol(C.sub.6- to C.sub.22-)ester, a vitamin ester,
salicylic acid, benzoic acid, lecithin, and mixtures thereof.
6. A surfactant composition according to claim 49 in the form of an
emulsion, characterized in that the co-amphiphiles is present in
solid form at 25.degree. C.
7. A surfactant composition according to claim 49 in the form of a
dispersion, characterized in that the co-amphiphiles is present in
liquid form at 25.degree. C.
8. A surfactant composition according to any one of claims 5 or 49,
characterized in that at least two different co-amphiphiles are
employed.
9. A surfactant composition according to claim 49, wherein at least
one co-amphiphiles is a C.sub.6- to C.sub.40-alcohol, a mono-, di-,
and triglyceride of C.sub.6- to C.sub.22-carboxylic acid, and
mixtures thereof.
10. A surfactant composition according to claim 9, characterized in
that the surfactant composition comprises 30 to 50 wt % of C.sub.6-
to C.sub.40-alcohol, 30 to 50 wt % of a mono-, di-, and
triglyceride of a C.sub.6- to C.sub.22-carboxylic acid, and
mixtures thereof, each referring to the gemini
surfactant/co-amphiphile(s) composition.
11. A surfactant composition according to claim 49 in the form of
an emulsion, characterized in that the surfactant composition can
be produced by a method (phase transfer temperature (PTT) method),
which includes at least the following step: combining (a) a
composition (a) comprising the gemini surfactant (A) wherein the
composition has a temperature X, with (b) a composition (b)
comprising the co-amphiphile (B) wherein the composition has a
temperature Y, the temperature Y being greater than temperature
X.
12. The surfactant composition of claim 11, characterized in that
the temperature Y is not more than 15.degree. C. higher than the
critical phase transfer temperature of the surfactant in
composition (b).
13. Surfactant compositions according to claim 12, characterized in
that the temperatures X and Y are different by at least 3.degree.
C.
14-15. (canceled)
16. A surfactant composition according to claim 14, characterized
in that the hydrophobic double group comprises a C.sub.6- to
C.sub.24-hydrocarbon residue each and/or the hydrophilic double
(head) group comprises an at least monoalkoxylated residue with a
sulfonic acid-, carboxylic acid-, phosphonic acid-, polyalcohol-,
or polyalkylene oxide group, or salt thereof.
17. A surfactant composition according to claim 49 characterized in
that the surfactant composition comprises 0.01 to 30 wt % of the
components (A) and (B), referring to the total composition.
18-31. (canceled)
32. The surfactant composition of claim 49 wherein said gemini
surfactants is present in an amount of from 10 to 60 wt %.
33. The surfactant composition of claim 49 wherein said gemini
surfactants is present in an amount of from 10 to 50 wt %.
34. The surfactant composition of claim 5 wherein said alcohol is a
C.sub.8- to C.sub.24-alcohol.
35. The surfactant composition of claim 5 wherein said carboxylic
acid is a C.sub.8- to C.sub.22-carboxylic acid.
36. The surfactant composition of claim 5 wherein 3 to 5 different
co-amphiphiles are employed.
37. The surfactant composition of claim 9 wherein said alcohol is a
C.sub.8- to C.sub.24-alcohol.
38. The surfactant composition of claim 10 wherein said alcohol is
a C.sub.8- to C.sub.24-alcohol.
39. The surfactant composition of claim 11 wherein said composition
(a) contains water.
40. The surfactant composition of claim 11 wherein said composition
(b) contains an oil component.
41. The surfactant composition of claim 12 wherein the temperatures
X and Y are different by at least 5.degree. C.
42. The surfactant composition of claim 17 wherein the surfactant
composition comprises 0.1 to 6 wt % of the components (A) and (B),
referring to the total composition.
43-48. (canceled)
49. A surfactant composition comprising (A) 1 to 70 wt %, referring
to components (A) and (B), of a gemini surfactant having the
general formula (A.II). ##STR16## wherein R.sup.1, R.sup.3 are
C.sub.5- to C.sub.25-alkyl group that can be branched, unbranched,
saturated, or unsaturated as far as not adjacently diunsaturated;
R.sup.2 is C.sub.1- to C.sub.12-alkylene; X, Y are
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.y--FR;
x+y.gtoreq.1, x: 0-15, y: 0-10; and FR is --SO.sub.3M,
--CH.sub.2--CO.sub.2M, --P(O)(OM).sub.2, H,
--C.sub.3H.sub.6SO.sub.3M, --CH.sub.2(CHOH).sub.4CH.sub.2OH,
insofar as x+y=0, wherein M=alkali, (alkyl)ammonium, alkanol
ammonium, H, or 1/2 alkaline earth. (B) referring to the remainder,
based on the total of components (A) and (B), one or more
co-amphiphile(s) having an HLB value of less than or equal to 6.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a surfactant composition of gemini
surfactants and one or more co-amphiphile(s), to a process for
preparing such composition, and to its uses, especially as
emulsifiers and dispersants.
[0003] 2. Description of the Prior Art
[0004] Mixtures of surfactants and co-amphiphiles and their use in
emulsions or dispersions are well known. These mixtures have been
designed for optimising the surfactant molecules pattern at the
phase boundaries. When making emulsions, it is often intended to
form liquid-crystalline, lamellar phases, which can be utilised to
stabilise the emulsion.
[0005] Proportionate mixtures of special surfactants and
co-amphiphiles are employed according to their applications. For
those applications which require a high electrolyte content in
aqueous solutions or emulsions/dispersions, ionic surfactants have
up to now been considered to be largely unsuitable. In order to
improve the selection of appropriate surfactants, efforts have been
made to quantify or classify their polarities, thus enabling a more
reliable assessment of the properties and application patterns. The
HLB concept and its variations is mentioned here as an example of a
simple approach.
[0006] Gemini surfactants, both as nonionic and cationic variants,
have been known for more than twenty years, but it was not earlier
than in the '90s that they stirred up a deeper interest. For a
survey of the state of the art, see R. Zana, "Dimeric (Gemini)
Surfactants" in Novel Surfactants Preparation, Applications and
Biodegradability, C. Holmberg (ed.), Marcel Dekker (1998), p.
241.
[0007] Most of the recent publications deal with ionic gemini
surfactants because these materials significantly enhance the
interfacial activity, for instance expressed in terms of the
critical micelle formation constant or the reduction in surface
tension of water, in comparison with conventional surfactants.
[0008] At first gemini surfactants were mainly recommended for use
in detergents and cleaning products.
[0009] JP-A 08/268,865 also describes the use of gemini surfactants
in cosmetic preparations. In the formulations disclosed therein
conventional anionic surfactants have been exchanged for anionic
gemini surfactants, which are considerably less irritant to the
skin, without laborious modification of the formulations.
[0010] EP-A-0 697 244 discloses amphoteric gemini surfactants,
which can also be mixed with other anionic, nonionic, cationic, or
amphoteric surfactants. Said surfactants are reported to be useful
in detergents. The gemini surfactants (gemini amides) described in
WO 95/19953 can be employed among others as components in customary
cleaning preparations. In WO 95/19955 gemini polyethers have been
disclosed as another class of gemini surfactants, which are useful
for the same application mentioned hereinbefore. Mixtures of
alkoxylated bisalkylphenol gemini surfactants and other surfactants
are known from WO 97/23449.
[0011] In JP-A 11/60430 and JP-A 11/60437 the use of anionic gemini
surfactants in cosmetics has been described. Reportedly, these
surfactants can also be combined with other surfactants.
[0012] However, in contrast to what might be expected due to the
substantial improvement in interfacial activity, no significant
increase in efficiency or distinct improvement of application
characteristics has been brought about by gemini surfactants as
direct substitutes for conventional surfactants. The meagre
advantage of such surfactant substitution cannot justify the effort
of incorporating an additional building element in the basic
structure.
SUMMARY OF THE INVENTION
[0013] It is an object of the present invention to provide a
composition containing gemini surfactants and auxiliaries
(hereinafter termed "surfactant composition"), which will allow to
utilise the known benefits of gemini surfactants in special uses in
the broadest possible spectrum of applications, thus opening up a
commercially interesting larger field.
[0014] According to the present invention, the problem has been
solved by providing surfactant compositions of at least one gemini
surfactant and at least one co-amphiphile having an HLB value of
less than 6, said surfactant composition containing from 1 to 70 wt
% of gemini surfactant and from 99 to 30 wt % of coamphiphile,
referring to the total quantity of gemini surfactant and
co-amphiphile. The preferred embodiments of the invention are set
out in the subordinate claims.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0015] It has been found that the surfactant compositions of the
invention containing gemini surfactants and co-amphiphiles not only
optimise specific application characteristics, but also present
considerable multifunctionality and greater efficiency, when
compared to mixtures of conventional (non-gemini) surfactants and
co-amphiphiles.
[0016] Multifunctionality is expressed for example by the
surprising fact that it is possible to disperse a hydrophilic or
hydrophobic pigment both in an oil phase and in a water phase
(emulsifying and dispersing effect), when using the very same
mixture of gemini surfactant and co-surfactant. With several of the
surfactant compositions of the invention the degree of
multifunctionality is even so high that one and the same surfactant
composition is both an excellent emulsifier and dispersant without
the need to adjust the respective emulsifier/dispersant system to
the particular application. With respect to its emulsifying effect,
the surfactant composition of the invention may be termed a gel
network emulsifier.
[0017] The oil-in-water (O/W) emulsions prepared with the aid of
the surfactant compositions of the invention are characterised by a
substantially smaller oil drop size, when applying the "phase
transfer temperature" method during production.
[0018] The surfactant compositions of the invention impart to the
emulsions or dispersions prepared therefrom a degree of electrolyte
stability which up to now has been unknown even with nonionic
systems. In comparison with known complex emulsifiers, an
electrolyte quantity which is greater by the factor 5 to 10 and
which results in the breakdown of conventional emulsions will not
produce this effect if the emulsions contain the components of the
invention. The emulsions or dispersions prepared from the
surfactant compositions of the invention remain stable at pH values
within a range from 3 to 12.
[0019] Furthermore, the surfactant compositions of the invention
have film-forming properties, which are particularly favourable
regarding the large variety of applications, for example skin
creams, UV protectants, or hair care products.
[0020] In addition to their technical functionality, the products
are exceptionally mild. For example, by addition of the surfactant
compositions of the invention to alkylether sulfates, alkylbenzene
sulfonates, and other anionic surfactants the irritation potential
of these substances can be distinctly reduced. The surfactant
compositions are also distinguished by their high affinity for
various types of interfaces. Besides the technical advantages
gained when formulating different products, also application
benefits have been found, such as improved combability of wet/dry
hair, antistatic features, and silky touch of the skin.
[0021] This surprising multifunctionality or universal
applicability has up to now been unknown both in individual
surfactants and combinations of conventional surfactants and
co-surfactants. It is now possible to distinctly simplify
formulations, shorten formulation development work, and improve
logistics. Furthermore, the application formulations thus made are
much more efficient.
[0022] For the purpose of the present invention the term "gemini
surfactant" is defined as a surface-active compound consisting of
at least (preferably) two surfactant units, i.e., one hydrophilic
head group and one hydrophobic group interlinked through at least
(preferably) one spacer in proximity to the head group. Gemini
surfactants are also termed dimer surfactants because of their
specific structure. There exist anionic, nonionic, cationic, and
amphoteric gemini surfactants, depending on the kind of head group.
However, in contrast to conventional surfactants, which are grouped
in the same way, gemini surfactants can also have combinations of
different head groups, mostly combinations of nonionic and ionic
groups.
[0023] The subject matter of the present invention relates to
surfactant compositions containing anionic, cationic, and/or
neutral gemini surfactants. Whenever ionic head groups are combined
with nonionic ones, the ionic head group shall be predominant in
the resultant gemini surfactant, such that combinations of a
nonionic head group and an anionic head group can be classified as
anionic gemini surfactant. The same applies to combinations of
nonionic head groups with cationic or amphoteric ones.
[0024] As to the surfactant compositions of the invention, it is
morphology (i.e., the relative arrangement of different structural
units, namely, hydrophilic groups, spacer, hydrophobic chains) that
is essential, the type of head group is not. Hence, the gemini
surfactants of the present invention have the following structure:
##STR1##
[0025] The preferred gemini surfactants used in the surfactant
compositions of the invention have nitrogen atoms at the link
between spacer, hydrophilic group, and hydrophobic group. More
preferably, the gemini surfactants have spacers with amine or amide
groups, but also spacers derived from dicarboxylic acids,
betainederived hydrophilic double head groups, optionally
presenting side groups obtained by alkoxylation, especially
ethoxylation, which head groups may bear sulfonic acid, phosphonic
acid, carboxylic acid, or alcohol groups, including polyalcohols,
each of which having hydrophobic chains with 5 to 25 carbon atoms,
which are branched or unbranched and may bear up to two
non-adjacent double bonds.
[0026] The following variants of gemini surfactant structures are
particularly useful for the surfactant compositions of the
invention. [0027] Variant A: Structures based on amide- or
amine-containing spacers [0028] A.I Gemini surfactants of the
general formula (A.I) according to WO 96/14926 ##STR2## [0029]
wherein the substituents have the following meanings: [0030]
R.sup.1, R.sup.3 C.sub.5- to C.sub.25-alkyl, branched or
unbranched, saturated, optionally unsaturated as far as not
adjacently diunsaturated; [0031] R.sup.2 C.sub.1- to
C.sub.12-alkylene; [0032] X, Y
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.y--FR;
x+y.gtoreq.1, x: 0-15, y: 0-10; and [0033] FR --SO.sub.3M,
--CH.sub.2--CO.sub.2M, --P(O)(OM).sub.2, H,
--C.sub.3H.sub.6SO.sub.3M; or --CH.sub.2(CHOH).sub.4CH.sub.2OH,
insofar as x+y=0, wherein M=alkali, (alkyl) ammonium, alkanol
ammonium, H, or 1/2 alkaline earth. [0034] A.II Gemini surfactants
having dicarboxylic acid-based spacers of the general formula
(A.II) in accordance with WO 96/25388 ##STR3## [0035] wherein the
substituents have the meanings as defined hereinabove by the
general formula (A.I). [0036] A.III Amphoteric gemini surfactants
of the general formula (A.III) in accordance with WO 97/31890
##STR4## [0037] wherein the substituents have the meanings as
defined hereinabove by the general formula (A.I). Gemini
surfactants of the general formula (A.III) are amphoteric
compounds, which can turn into cationic ones if the ambient medium
is acidic. [0038] Variant B: Structures based on amide- or
amine-containing spacers [0039] B.I Gemini surfactants of the
general formula (B.I) in accordance with DE 19622612 or JP-A
10-175934 ##STR5## [0040] wherein the substituents have the
following meanings: [0041] R.sup.1, R.sup.3 C.sub.5- to
C.sub.25-alkyl, branched or unbranched, saturated, optionally
unsaturated as far as not adjacently diunsaturated; [0042] R.sup.2
C.sub.1- to C.sub.12-alkylene; [0043] A CHR.sup.4, CH.sub.2,
C.sub.2H.sub.4, C.sub.3H.sub.6, C.sub.4H.sub.8; [0044] R.sup.4
aminocarboxylic acid radical; and [0045] M alkali, (alkyl)
ammonium, alkanol ammonium, H, or 1/2 alkaline earth. [0046] B.II
Gemini surfactants of the general formula (B.II) in accordance with
EP 0 708 079 ##STR6## [0047] wherein the substituents have the
meanings as defined hereinabove by the general formula (B.I) and
[0048] R.sup.5, R.sup.6 represent C.sub.6- to C.sub.36-alkyl,
branched or unbranched, saturated, optionally unsaturated as far as
not adjacently diunsaturated; [0049] X is an alkylene- or
alkenylene group having from 1 to 6 carbon atoms, which may be
substituted with a hydroxyl group or a sulfonic acid group or a
carboxy group; [0050] Y.sup.1 is a sulfonate- or sulfate group or a
carboxyl group, and [0051] Y.sup.2 represents a hydroxyl group, a
sulfuric acid residue, or --O--(CO)X--COOH. [0052] B.III Gemini
surfactants of the general formula (B.III) according to
JP-A-8-311003 ##STR7## [0053] wherein the substituents have the
meanings as defined hereinabove by the general formula (B.I) and
[0054] FG represents --COOM or --SO.sub.3M. [0055] B.IV Gemini
surfactants of the general formula (B.IV) according to JP-A
11-60437 ##STR8## [0056] wherein the substituents have the meanings
as defined hereinabove by the general formulas (B.I) and (B.II) and
[0057] AO represents alkylene oxide units, i.e. ethyleneglycol-,
propyleneglycol-, and butyleneglycol ether units, alone or arranged
randomly or blockwise, wherein n=1 to 20, and [0058] Z is
--SO.sub.3M, --C.sub.2H.sub.4SO.sub.3M, --C.sub.3H.sub.6SO.sub.3M,
--P(O)(OM).sub.2 or --CH.sub.2--COOM, --C.sub.2H.sub.4--COOM.
[0059] Variant C: Structures based on amide- or amine-containing
spacers [0060] C.I Gemini surfactants of the general formula (C.I)
according to EP 0-697 244, ##STR9## [0061] wherein the substituents
have the following meanings: [0062] R.sup.1 C.sub.5- to
C.sub.25-alkyl, branched or unbranched, saturated, optionally
unsaturated as far as not adjacently diunsaturated,
hydroxy-substituted or perfluorinated; [0063] R.sup.2 C.sub.1- to
C.sub.12-alkylene or hydroxy-substituted derivatives thereof;
[0064] B an amide group [--C(O)N(R.sup.2)-- or --N(R.sup.5)C(O)--],
a carboxyl group [--C(O)O-- or --OC(O)--], a polyether group
[--O(R.sup.6--O).sub.x--]; [0065] R.sup.5 C.sub.1- to C.sub.4-alkyl
or hydroxy-substituted alkyl or H; [0066] R.sup.6 C.sub.2- to
C.sub.4-alkylene; [0067] x a number from 1 to 20; [0068] R.sup.3
C.sub.1- to C.sub.12-alkyl or hydroxy-substituted derivatives
thereof, [0069] R.sup.7-D-R.sup.7 or a polyether group
[--O(R.sup.6--O).sub.x--]; [0070] R.sup.7 C.sub.1- to
C.sub.6-alkylene or hydroxy-substituted derivatives thereof; [0071]
D --O--, --S--, --N(R.sup.8)--; [0072] R.sup.4 alkylene or
alkylaryl having from 1 to 12 carbon atoms or the
hydroxy-substituted derivatives or R.sup.9-D.sup.1-R.sup.9; [0073]
R.sup.8 C.sub.1- to C.sub.12-alkyl or hydroxy-substituted alkyl or
H or R.sup.9-D.sup.1-R.sup.9; [0074] R.sup.9 C.sub.1- to
C.sub.6-alkylene or hydroxy-substituted derivatives thereof or
aryl; [0075] D.sup.1 -O--, --S--, --SO.sub.2--, --C(O)--,
[--O(R.sup.7--O).sub.x--], (R.sup.10).sub.t[N(R.sup.10)].sub.z, or
aryl; [0076] R.sup.10 C.sub.1- to C.sub.12-alkyl or
hydroxy-substituted alkyl or H or aryl; [0077] t, z are
independently a number from 1 to 4, and [0078] Y is independently
--SO.sub.3H, O--SO.sub.3H, --OP(O)(OH).sub.2, --P(O)(OH).sub.2,
[0079] --COOH, --CO.sub.2--C.sub.6H.sub.4--SO.sub.3H and the salts
thereof. [0080] C.II Gemini surfactants of the general formula
(C.II) according to EP 0 697 245 ##STR10## [0081] wherein the
substituents have the meanings as defined hereinabove by the
general formula (C.I) and [0082] R.sup.11 is C.sub.5- to
C.sub.23-alkyl, branched or unbranched, saturated, optionally
unsaturated as far as not adjacently diunsaturated,
hydroxy-substituted or perfluorinated or R.sup.14--B--R.sup.2;
[0083] R.sup.14 is C.sub.1- to C.sub.12-alkyl, branched or
unbranched, saturated, optionally unsaturated as far as not
adjacently diunsaturated, or the hydroxy-substituted derivatives;
[0084] R.sup.12 means C.sub.1- to C.sub.12-alkylene, branched or
unbranched, saturated, optionally unsaturated as far as not
adjacently diunsaturated, or the hydroxy-substituted derivatives,
or an amide group [--C(O)N(R.sup.2)-- or --N(R.sup.5)C(O)--], a
carboxyl group [--C(O)O-- or --OC(O)--], a polyether group
[--O(R.sup.6--O).sub.x--] or R.sup.9-D.sup.1-R.sup.9 and [0085] A
is --CR.sup.6.dbd. or --N.dbd., if whenever A is equal to --N.dbd.,
R.sup.11 represents R.sup.14--B--R.sup.2. [0086] C.III Gemini
surfactants of the general formula (C.III) according to DE 4227391
and DE 19608117 ##STR11## [0087] wherein the substituents have the
meanings as defined hereinabove by the general formulas (C.I) and
(C.II) and [0088] R.sup.21 represents C.sub.5- to C.sub.23-alkyl,
branched or unbranched, saturated, optionally unsaturated as far as
not adjacently diunsaturated; [0089] R.sup.22, R.sup.24 are
C.sub.1- to C.sub.6-alkylene; [0090] R.sup.23 is methyl, ethyl,
propyl, or a polyether group [--O(R.sup.6--O).sub.x--]. [0091]
Variant D: [0092] D.I Gemini surfactants of the general formula
(D.I) according to U.S. Pat. No. 5,863,886 ##STR12## [0093] wherein
the substituents have the following meanings: [0094] R, R.sup.1
C.sub.5- to C.sub.30-alkyl, branched or unbranched, saturated,
optionally unsaturated as far as not adjacently diunsaturated,
hydroxy-substituted or perfluorinated; [0095] R.sup.2 C.sub.1- to
C.sub.10-alkylene, arylene, and hydroxy-substituted derivatives, a
polyether [--O(R.sup.4O).sub.x--], --S--, --SO.sub.2--, --O--,
--S--S--, [0096] O--R.sup.5--O--, or --S--R.sup.5--S--; variable
for a direct bond between the two .alpha.-carbons; [0097] R.sup.4
C.sub.2- to C.sub.4-alkylene; [0098] R.sup.5 C.sub.1- to
C.sub.10-alkylene, arylene or alkyl arylene, --N(R.sup.6)--, or
--(NR.sup.6)--R.sup.7--(NR.sup.6)--; [0099] R.sup.6 C.sub.1- to
C.sub.6-alkyl; [0100] R.sup.7 C.sub.1- to C.sub.6-alkyl, wherein
R.sup.7 and R.sup.6 can also be part of a heterocyclic ring; [0101]
X polyether [--O(R.sup.4O).sub.x--], wherein x is a number from 1
to 30, --O--, NZ; [0102] Z C.sub.1- to C.sub.10-alkyl, aryl,
alkylaryl, or H, and [0103] Y, Y.sup.1, are independently H,
--CH.sub.2--COOH and salts, a hydrocarbon radical having at least
two hydroxyl groups, such as erythrose, threose, ribose, arabinose,
xylose, fructose, lyxose, allose, altrose, glucose, mannose,
galactose and mixtures thereof. [0104] D.II Gemini surfactants of
the general formula (D.II) ##STR13## [0105] wherein the
substituents have the meanings as defined hereinabove by the
general formula (D.I) and [0106] AO means --C(O)--,
--C(O)--[--O(R.sup.4O).sub.x--],
--CH.sub.2--[--O(R.sup.10).sub.x--], --CH.sub.2--O--; [0107] T,
T.sup.1 are independently --OM, --H, --CH.sub.3, --C.sub.2H.sub.5,
--SO.sub.3M, --CH.sub.2COOM, [0108] --C.sub.2H.sub.4--COOM,
--C.sub.3H.sub.6--SO.sub.3M, --O--P(O)(OM).sub.2 and [0109] M is
alkyli, 1/2 alkaline earth, ammonium, mono-, di-,
trialkanolammonium, or H. [0110] D.III Gemini surfactants of the
general formula (D.III) according to WO 96/16930 ##STR14## [0111]
wherein the substituents have the meanings as defined hereinabove
by the general formulas (D.I) and (D.II) and [0112] R.sup.8 is
NYY.sup.1, --O(R.sup.4O).sub.xH or
--O(R.sup.4O).sub.x--C(O)--CHR--CHR.sup.1--C(O)NYY.sup.1. [0113]
D.IV Gemini surfactants of the general formula (D.IV) according to
WO 96/25384 ##STR15## [0114] wherein the substituents have the
meanings as defined hereinabove by the general formulas (D.I),
(D.II), and (D.III) and [0115] t is an integer from 1 to 100,
preferably 1 to 20, most preferably 1 to 4.
[0116] The co-amphiphiles employed according to the present
invention have an HLB value of <6, calculated by the known
formula HLB=E/5 (E means weight percentage of the hydrophilic
moiety of the molecule).
[0117] As to the use of surfactant compositions of the present
invention in emulsions, those co-amphiphiles which are solid at
room temperature (25.degree.) are particularly suitable, whereas
for use in dispersions those co-amphiphiles which are liquid at
room temperature are preferred. Examples of these preferable
co-amphiphiles include C.sub.6- to C.sub.40-alkyl alcohols,
especially C.sub.8- to C.sub.24-alkyl alcohols, most preferably
cetyl alcohol or behenyl alcohol, which can be branched or
unbranched, saturated or non-adjacently mono- to triunsaturated,
acyclic or alicyclic, non-neutralized C.sub.6- to
C.sub.24-alkylcarboxylic acids, preferably C.sub.8- to
C.sub.22-alkylcarboxylic acids, which can be branched or
unbranched, saturated or non-adjacently mono- to triunsaturated,
acyclic or alicyclic, alkylaryl derivatives, sorbitan esters
(C.sub.6 to C.sub.22), methylglucoside esters (C.sub.6 to
C.sub.22), sugar esters (C.sub.6 to C.sub.22), mono-, di-, and
triglycerides of C.sub.6- to C.sub.22-carboxylic acids or mixtures
thereof, glycerol mono-di-stearate being particularly preferred,
branched or unbranched, saturated or non-adjacently mono- to
triunsaturated, mono- and di-glycerides of the aforementioned acids
and their derivatives which have been further esterified with
lactic acid and/or citric acid, C.sub.6- to C.sub.22-polyglycerol
esters, C.sub.6- to C.sub.22-propyleneglycol esters, and also
vitamin esters (e.g. vitamin E acetate, vitamin A palmitate),
salicylic acid, benzoic acid, lecithins (of vegetable oils or
animals). The alcohols, acids, and mono- and diglycerides of the
aforementioned carboxylic acids are especially preferred.
[0118] The surfactant compositions of the invention are pre-sent as
mixtures of from 1 to 70 wt %, preferably from 5 to 60 wt %, most
preferably from 5 to 40 wt % of gemini surfactant or of a mixture
of appropriate gemini surfactants and, accordingly, 99 to 30 wt %,
preferably 95 to 40 wt %, most preferably 95 to 60 wt % of
co-amphiphile. Most preferably, the surfactant compositions contain
the aforementioned constituents in the quantities specified
hereinabove. Within the mixing ratios of gemini surfactant(s) and
co-amphiphile as specified hereinabove, it is also possible to
employ mixtures of different co-amphiphiles, e.g. of up to five,
preferably of three. Especially preferable mixtures are those of
distinctly hydrophobic co-amphiphiles and slightly hydrophilic
ones. Their proportions depend on the hydrophilicity of the gemini
surfactant, i.e. if the gemini surfactant is very hydrophilic, the
portion of hydrophobic co-amphiphile can be as much as 30 to 60% of
the co-amphiphile quantity in the surfactant composition of the
invention, with the co-amphiphiles having a difference in HLB value
of greater than 2 units.
[0119] Preferable mixtures are those of long-chain alcohols
(C.sub.6- to C.sub.40-alcohol, with increasing preference for
C.sub.8- to C.sub.24-, C.sub.14- to C.sub.36-, or C.sub.14- to
C.sub.24-alcohol), such as cetyl alcohol or behenyl alcohol,
glycerol mono-di-stearate (GMS), and glycerol monostearate
esterified with citric acid, or according to another embodiment of
the surfactant composition of long-chain alcohols, such as cetyl
alcohol or behenyl alcohol or erucic alcohol, GMS, and stearic
acid, the mixtures of behenyl alcohol, GMS, and glycerol
monostearate esterified with citric acid are most preferable.
[0120] Preferable surfactant compositions independently have
besides [0121] the gemini surfactant, preferably in quantities of
from 5 to 25 wt %, most preferably from 10 to 20 wt %, referring to
the gemini surfactant/co-amphiphile(s) composition, at least two,
preferably three of the different co-amphiphiles as defined
hereinafter: [0122] (a) one or more long-chain alcohol(s): [0123]
C.sub.6- to C.sub.40-alcohol, with increasing preference for
C.sub.8- to C.sub.24-, C.sub.14- to C.sub.36--, or C.sub.14- to
C.sub.24-al-cohol, [0124] (b) one or more long-chain acid(s):
[0125] C.sub.6- to C.sub.24-, preferably C.sub.8- to
C.sub.22-carboxylic acid, [0126] (c) one or more ester(s)/partial
ester(s) of a polyol with one or more mono- or polycarboxylic
acid(s): [0127] sorbitan(C.sub.6- to C.sub.22-)ester, [0128]
methylglucoside(C.sub.6- to C.sub.22-)ester, [0129] sugar(C.sub.6-
to C.sub.22-)ester, [0130] mono-, di-, and triglyceride of a
C.sub.6- to C.sub.22-carboxylic acid, [0131] derivative (esterified
with lactic acid or citric acid) of the mono- and diglycerides of
C.sub.6- to C.sub.22-carboxylic acid, [0132] polyglycerol(C.sub.6-
to C.sub.22-)ester, [0133] propyleneglycol(C.sub.6- to
C.sub.22-)ester, [0134] vitamin ester, [0135] (d) and the following
additional co-amphiphiles: [0136] salicylic acid, [0137] benzoic
acid and/or [0138] lecithin.
[0139] According to another embodiment, the surfactant compositions
of the present invention preferably have at least two, more
preferably at least three of the co-amphiphiles specified
hereinbelow: [0140] (a) one or more long-chain alcohol(s) as
defined hereinabove under (a) in quantities of from 30 to 50 wt %,
[0141] (c1) a glycerol derivative, e.g. a mono-, di-, and
triglyceride of C.sub.6- to C.sub.22-carboxylic acid, or a compound
with similar HLB values, in quantities of from 30 to 50 wt %, or
[0142] (b)(c2) a derivative (esterified with lactic acid or citric
acid) of the mono- and diglycerides of C.sub.6- to
C.sub.22-carboxylic acid and/or a C.sub.6- to C.sub.22-carboxylic
acid in quantities of from 5 to 25 wt %, preferably from 10 to 20
wt %, each based on the gemini surfactant/co-amphiphiles
composition.
[0143] Preferably, the long-chain alcohol is at least one of the
co-amphiphiles employed herein, and an ester of a polyol with one
or more mono- or polycarboxylic acid(s), preferably with 6 to 22
carbon atoms, is the other (an additional) co-amphiphile.
[0144] Preferable co-amphiphiles have independently been specified
hereinbelow in the patent claims.
[0145] For example, when using five co-amphiphiles, the composition
of the invention preferably contains besides the gemini surfactant
the following co-amphiphiles in quantities of from 5 to 25 wt %,
preferably from 5 to 20 wt %: TABLE-US-00001 co-amphiphile 1
long-chain alcohol as defined under (a), in quantities of from 20
to 50%, preferably from 20 to 35 wt %, co-amphiphile 2 an
ester/partial ester of a polyol with one or more mono-or
polycarboxylic acid(s) as defined under (c), especially GMS or a
compound with a comparable HLB value, in quantities of from 20 to
50 wt %, preferably from 20 to 35 wt %, co-amphiphile 3 5 to 25%,
preferably 10 to 20 wt %, co-amphiphile 4 5 to 25%, preferably 10
to 20 wt %, and co-amphiphile 5 5 to 25%, preferably 10 to 20 wt
%.
[0146] According to a particularly preferable embodiment of the
present invention, the composition is as follows: TABLE-US-00002
Gemini surfactant 5 to 15 wt % Glycerolmono-distearate 30 to 40 wt
% Behenyl alcohol 35 to 45 wt % and Glycerylstearate citrate 10 to
20 wt %.
[0147] The gemini surfactant employed herein is most preferably a
type (a) one as defined hereinabove.
[0148] Without limiting the present invention to the mechanism set
forth herein, it is assumed that the surfactant compositions of the
invention show a surprisingly pronounced tendency to form distinct,
liquid-crystalline lamellar phases or vesicular structures with
exceptional interfacial elasticity, thus allowing to prepare in a
very efficient way finely dispersed, stable emulsions or very
stable dispersions. The liquid-crystalline lamellar phases obtained
by the aid of the surfactant compositions of the invention occupy
very large spaces in the phase diagrams of the application
formulations. These liquid-crystalline lamellar phases can
stabilize as a gel network the respective formulations and/or can
be utilized as a viscosity-imparting third phase for adjusting
viscosity and spreading of the individual systems.
[0149] In O/W emulsions, i.e. in the presence of oil and water, the
surfactant composition of the invention forms a third phase,
depending on the mixing ratio. This third phase is a
three-dimensional network, which stabilizes the separation between
oil and water (water hardness is negligible when using anionic
gemini surfactants) and increases the viscosity of the mixture.
Hence, stabilization is further enhanced so that for example
"reaming" is considerably retarded or even completely suppressed
with optimal formulations. The softening point of the gel network
is important for the stability of a gel network-stabilized
emulsion. The softening point is heavily influenced by the melting
point of the alcohol employed as a co-amphiphile. Therefore, only
long-chain alcohols are employed herein.
[0150] It has been unexpectedly found with the surfactant
compositions of the present invention that the very same
combination can be utilized both as an extremely effec-tive
emulsifier with respect to the polarity of the oil/oil mixtures
employed (including silicone oil) and as a very efficient
dispersant with respect to the surface of the dispersed pigment
(hydrophilically or hydrophobically coated) and to the medium
(dispersed in oil or water). It has so far been argued by those
skilled in the art that different tasks, e.g. dispersion of a
hydrophilic pigment in water or dispersion of a hydrophilic
surfactant in oil, require individual solutions, i.e. individual
dispersant or emulsifier combinations of gemini surfactant plus
co-amphiphile(s).
[0151] It has also been surprisingly found that the surfactant
compositions of the invention show very high pH- and electrolyte
tolerances, thus reducing the lipid peroxide concentration, when
using said mixture in a cream or lotion. Combinations with anionic
surfactants have so far been considered very sensitive to
electrolytes in formulations.
Process for Preparing the Aforesaid Surfactant Compositions
[0152] The phase transfer temperature method (PTT method) is a
particularly preferable method of producing the surfactant
compositions of the invention as emulsions with extremely small
droplet size of the discontinuous phase (e.g. <1 .mu.m). The PTT
method has been modeled on the phase inversion method of producing
ethoxylated surfactants (K. Shinoda, H. Saito, J. Colloid Interface
Sci., 34 (1969) p. 238, incorporated by reference herein) insofar
as this method, too, makes use of phase transition with extremely
low interfacial tension. The phase transition is characterized by
transition from a micellar phase to a predominantly lamellar one.
The co-amphiphile is combined shortly above the critical
temperature (defined by melting point and solubility of the
co-amphiphile in the oil phase) with the phase, which contains the
aqueous gemini surfactant and which temperature is shortly below
the critical one. When mixing the two phases, the co-amphiphile is
probably absorbed to a higher degree in the micelles of the gemini
surfactants. This effect is probably accelerated by the decreasing
solubility in the oil phase as the temperature drops. The mixture
thus obtained displays a strong tendency to form a
liquid-crystalline, lamellar phase, which in fact is rapidly formed
due to the rapidly growing micelles, thus resulting in surprisingly
small and stable oil droplets with diameters according to this
invention of preferably <1 .mu.m.
[0153] For the production of surfactant compositions according to
the present invention, this method is much more suitable than
conventional emulsifying methods (see survey by J. Britto, Euro
Cosmietics, 7-8 (1998), p. 30). However, when employing the PTT
method for mixtures of conventional surfactants and co-amphiphiles,
their properties normally will not improve.
Examples of Applications
[0154] Examples of practicable applications are given below by way
of illustration. The surfactant compositions of the present
invention are preferably used as emulsifying or dispersing aids, as
additives for conventional anionic (non-gemini) surfactants, or as
additives for skin and hair cleaning formulations. The surfactant
compositions of the invention are suitable for formulating O/W--,
W/O-emulsions (e.g. with use of lecithin as a co-amphiphile) and
microemulsions.
[0155] In addition, they are useful in cosmetics, body care and
dermatological products, agrochemicals, coating materials, such as
paints and lacquers (as dispersant, primer agent, additive for
improving the dispersion and droplet size distribution of the
organic phase in water-based lacquers), or in (printing) inks.
Moreover, the emulsifying and dispersing properties of the
surfactant compositions of the present invention make them
appropriate for facilitating or improving pharmaceutical
applications, e.g. for the controlled release of
pharmaceuticals.
[0156] Hence, a special embodiment of the instant invention relates
to cosmetic and dermatological preparations, such as cleaning
emulsions, face and body care preparations, hair and scalp care
products, mouth and teeth hygienical preparations, cosmetic and
dermatological sun-screen products, and cosmetic deodorants.
[0157] The surfactant compositions of the invention are useful in
the following formulations of body care, cosmetic, or
dermatological preparations: pump sprays, aerosol sprays, creams,
ointments, tinctures, lotions, nail care products (e.g. nail
varnish, nail varnish remover, nail balm), body lotions, aftershave
preparations, skin clarifiers, tanning creams, water-resistant
sunscreen creams or lotions, beauty cosmetics (lip sticks,
eyeliners), shampoos, antidandruffs shampoos, hair treatment
products, hair conditioners, hair rinses, baby shampoos, permanent
wave preparations, hair relaxer formulations (e.g. relaxer kits for
removing ringlets), washing gels, shower/bathing gels and
additives, handwash lotions, deodorants (e.g. rollon, stick,
spray), dental care products, denture cleaners, gargles, foam
baths, oil baths, oil foam baths, makeup removers, especially eye
makeup removers, face cleaning creams, hair creams (pomades),
moisturizing creams, skin care creams, such as daytype creams (with
or without sunscreen agent), foot creams, liposome-containing gels,
hair conditioning gels, depilatories (e.g. in cream form), shaving
gels or foams, massage creams, cosmetic masks, foundation creams,
hair-curling preparations, hair dyes, bar soap (combibar type),
synthetic soaps (syndets), and liquid handwash soaps.
[0158] Examples of other components, which can be combined with the
surfactant compositions of the present invention in body care or
cosmetic preparations, include alkyl sarcosinates, cellulose- and
guar derivatives, aromatic oils, lavender-, aniseed-, rosemary-,
spruce-, and larch oil, tea-tree (melaleuca alternifolia) oil, or
calendula oil, evening-primrose (oenothera biennis) oil, mouth care
aromatic oils (e.g. "Dragoco ZM 0065"), perfume oils, cosmetic
oils, such as avocado-, jojoba oils, or aloe vera; dialkylated
acetic acid, UV absorbers (as defined by EU directive 76/768/CEE
and its appendices and amendments), dihydroxyacetone, benzophenone,
octyltriazone, methoxycinnamic acid and the derivatives thereof,
melanine and its derivatives, long-chain dialkyl ethers,
methylbenzylidene camphor, esters of salicylic acid, hyaluronic
acid and its derivatives, cyclodextrines (void, e.g. as an odor
inhibitor, or packed, e.g. with fragrances and/or drugs), vitamins,
such as vitamin A or E, vitamin derivatives, such as vitamin A
palmitate, squalane, squalene, .beta.-carotene and other dyestuffs,
tocopherol and tocopherol derivatives (e.g. tocopherol acetate),
retinyl palmitate, bisabolol, dipanthenol, ascorbic acid,
antioxidants, vegetable steroids (e.g. ergosterol and
.beta.-sitosterol) and their derivatives, cholesterol and its
derivatives, parabenes and their derivatives (e.g. methyl-, ethyl-,
propyl- and butyl parabene), pcarlescent agents, anti-inflammatory
agents, ceramides, pseudoccramidcs, imidazolidinyl urea,
diiso-arachidyl dilinoleate, polymerse (e.g. polyacrylamides,
carboxyvinyl polymers, maleic anhydride-oleate copolymers,
polyethyleneglycol mono- or -diesters, polyvinyl-pyrrolidone,
polysaceharides, polyacrylates, fluorinated hydrocarbons), cationic
polymers (e.g. diethyldiallyl ammonium chloride/acrylamide
copolymers, antiperspiration agents (e.g. aluminium- or circonium
salts), citric acid, lactic acid, octylmethoxycinnamate,
phospholipids, sodium pyrrolidone carboxylate, gelatin, alginates,
albumin, collagen and its derivatives, beeswax, wax esters of
long-chain carboxylic acids (branched or unbranched) and long-chain
alcohols (branched or unbranched), dimethyl siloxanes (acyclic,
cyclic, volatile to oily), phenyltrimethicone, xanthane rubber,
starch derivatives, glycerol, ascorbic acid, polyethyleneglycols,
such as their mono- and dicarboxylic acid esters, fatty acid mono-,
-di-, and -triglycerides and their derivatives (-sulfates,
-citrates, -lactylates, -lactates, -tartrates), carnauba wax,
lecithin, chlorohexidine salts, benzethonium chloride, benzalkonium
chloride, triclosane, triclocarbane, methylchloroisothiazoline,
methylisothiazoline, chloroxylenol, DMDM-hydantoin,
alkyltrimethylammonium-bromide, salicylic acid and its derivatives,
inosite derivatives, acylated ethylenediamine derivatives,
colorants approved for cosmetic applications (as defined in the
publication "Kosmetische Farbernittel" [Cosmetic Colorants] by the
Colorants Commission of the German Society for the Advancement of
Scientific Research, Verlag Chemie, Weinheim (1984), p. 81 ff.) and
alcohols of C.sub.6- to C.sub.24-, guerbet alcohols and -acids.
[0159] Further constituents are:
[0160] antioxidants, e.g. selected from the group of amino acids
(e.g. glycerol, histidine, tyrosine, tryptophane) and their
derivatives, imidazoles (e.g. urocanine acid) and their
derivatives, peptides, such as DL-carnosine, D-carnosine,
L-carnosine, and their derivatives (e.g. "Anserin X"), carotinoids,
carotenes (e.g. .alpha.-carotene, .beta.-carotene, lycopine) and
their derivatives, liponic acid and its derivatives (e.g.
dihydroliponic acid), aurothioglucose, and other thiols (e.g.
thioredoxine, glutathione, cysteine, cystine, cyftamine and their
glycosyl-, N-acetyl-, methyl-, ethyl-, propyl-, amyl-, butyl-, and
lauryl-, palmitoyl-, oleyl-, linoleyl-, cholesteryl-, and glyceryl
esters) and the salts thereof, dilaurylthio-dipropionate,
distearylthiodipropionate, thiodipropionic acid and its derivatives
(esters, ethers, peptides, lipids, nucleotides, nucleosides and
salts) and sulfoximine compounds, homocysteine sulfoxiniine,
buthionine-sulfones, penta-, hexa-, heptathioninesulfoxiniine) in
very small compatible quantities, and also (metal-)-chelators (e.g.
.alpha.-hydroxyfatty acids, palmitic acids, phytinic acids,
lactoferrinic-, -hydroxy acids (e.g. citric acid, lactic acid,
malic acid, humic acid, bile acid), bile extract, bilirebine,
biliverdine, EDTA, and their derivatives, unsaturated fatty acids
and their derivatives (e.g. .gamma.-linolenic acid, linoleic acid,
oleic acid, folic acid and their derivatives), ubiquinone and
ubiquinol and their derivatives, vitamin C and derivatives (e.g.
ascorbyl palmitate, Mg-ascorbyl phosphate, ascorbyl acetate),
tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and
derivatives (vitamin A palmitate) and conylcrylbenzoate of benzoic
resin, rufinic acid and its derivatives, ferulic acid and its
derivatives, butylhydroxytoluene, butylhydroxyanisol,
nordihydroguajak uric acid, nordihydroguajaret acid,
trihydroxybutyrophenone, uric acid and its derivatives, mannose and
its derivatives, zinc and its derivatives (e.g. Zn0, ZnS0.sub.4),
selenium and its derivatives (e.g. selenium methionine), stilbenes
and their derivatives (e.g. stilbene oxide, transstilbene oxide)
and the derivatives (salts, esters, ethers, sugars, nucleotides,
nucleosides, peptides, and lipids) of the aforementioned active
agents. The antioxidants (one or more compound(s)) in the
preparations are preferably used in quantities of from 0.001 to 30
wt %, more preferably from 0.05 to 20 wt %, most preferably from 1
to 10 wt %, referring to the total quantity of the preparation.
[0161] If the antioxidant(s) is (are) vitamin E and/or its
derivatives, the preferable concentration is from 0.001 to 10 wt %,
referring to the total quantity of the formulation. If the
antioxidant(s) is (are) vitamin A or its derivatives or carotenes
or their derivatives, the preferable concentration is from 0.001 to
10 wt %, referring to the total quantity of the formulation.
[0162] Further constituents are:
[0163] UVB filters (oil-soluble or water-soluble), examples of
oil-soluble substances include: 3-benzylidene camphor and its
derivatives, e.g. 3,4,4-trimethylbenzylidene camphor,
4-aminobenzoic acid derivatives, preferably 4-dimethylaminobenzoic
acid (2-ethylhexyl)ester, 4-dimethylamino-benzoic acid-amylester,
esters of cinnamic acid, prefer-ably 4-methoxycinnamic
acid(2-ethylhexyl)ester, 4-meth-oxycinnamic acid isopentyl ester;
esters of salicylic acid, preferably salicylic
acid(2-ethylhexyl)ester, salicylic acid(4-isopropylbenzyl)ester,
salicylic acid homomethyl ester; derivatives of benzophenone,
preferably 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxy-methylbenzophenone,
2,2'-dihydroxy-4-methoxybenzo-phenone; esters of benzylmalonic
acid; examples of useful water-soluble substances include
2-phenylbenzimidazole-5-sulfonic acid and its salts, e.g. sodium-,
potassium-, or triethanol ammonium salts, sulfonic acid derivatives
of benzophenones and their salts, sulfonic acid derivatives of
3-benzylidene camphor and their salts.
[0164] UVA flitters, preferably derivatives of dibenzoyl ethane or
inorganic pigments (especially Zn0), which are usually present in
cosmetic and/or dermatologic preparations.
[0165] For the protection of the skin from UV rays (UVA and UVB),
it is also customary to employ inorganic pigments in cosmetic
preparations, such as oxides of titanium, zinc, iron, zirconium,
silicon, manganese, aluminium, cerium, and mixtures thereof, and
combinations (e.g. Ti-- and Fe oxides), wherein the oxides are the
active agents. In general, the aforementioned metal oxides have a
hydrophilic (e.g. glycerol) or a hydrophobic coating, e.g. alkyl
silanes or metal soaps.
[0166] Furthermore, the surfactant compositions of the invention
are useful as additives, e.g. emulsifiers, or application parameter
additives. They can be utilized in pesticides, especially
fungicides, herbicides (e.g. with active agents like glyphosates or
sulfosates), insecticides, nematocides, acaricides, and growth
regulators. They emulsify the active agents to form stable sprays,
which allow excellent wetting of the treated objects and con
trolled release of the active substances for a prolonged
period.
[0167] The surfactant compositions of the invention can also be
used in decoction agents for cotton (scouring), raw wool
detergents, milling agents, levelling agents, melting and preparing
agents, resisting agents, reviving agents, dispersions,
antielectrostatic agents, detaching agents, animal skin degreasing
agents, tanning auxiliaries, and dressing/currying agents.
[0168] The surfactant compositions of the invention are also useful
in disinfectants, wherein they can be combined with any customary
disinfecting substances, such as phenols, cresols, chlorohexidine
salts, benzethonium chloride, benzalkonium chloride, triclosane,
triclocarbane, methylchloroisothiazolidine, chloroxylenol,
DMDM-hydantoin, and alkyl trimethyl ammonium bromide.
[0169] Moreover, the surfactant compositions of the invention can
be employed as dispersants in coating materials. For example, they
effectively disperse and stabilize pigments in waterdilutable
paints. Examples of dispersible in organic pigments include
titanium oxide, iron oxide, cerium oxide, aluminium oxide, calcium
carbonate, calcium phosphate, talc powder, kaolin, barium sulfate,
aluminium- and zirconium salts, zinc oxide, silicates, and
alumosilicates. Examples of organic pigments include phthalocyanine
green and -blue, carbon black, and graphite. The surfactant
compositions of the invention can also be employed in emulsion
paints, wherein they disperse pigments and polymeric binder
particles, stabilize the emulsion, and improve substrate wetting,
e.g. in primers. In addition, the surfactant compositions of the
invention are useful as dispersants and/or stabilizers in
(printing) inks.
[0170] The surfactant compositions of the invention are also
suitable as dispersants in therapeutical preparations. These
applications are similar to those of cosmetics (creams, ointments,
lotions, etc.).
[0171] Yet another application of the surfactant compositions of
the instant invention is in emulsion- or suspension polymerization,
e.g. for producing (meth)acrylate-, vinylacetate-, or
vinylpropionate emulsions for paints or adhesives, or (co)polymer
emulsions of acrylamide, acrylic acid, acrylates, acrylonitrile,
maleic anhydride, styrene and/or butadiene, which are produced by
radical-initiated polymerization, e.g. with azoisobutyronitrile as
a starter.
[0172] Prior to use in any of the aforementioned applications, the
surfactant compositions of the invention can also be mixed with
other components. These additional components (or additives) can be
admixed prior to use or insitu.
[0173] Additives can be surfactants or completely different
constituents usually employed in formulations, agents, mixtures,
prepartions etc. for the respective applications. These additives
are specified hereinbelow. The expert knows which one is
appropriate for the respective application or formulation. Examples
of preferable additives include enzymes, enzyme stabilizers,
bleaching systems, chelating agents, optical brighteners, and foam
inhibitors.
[0174] Besides gemini surfactants, the surfactants specified
hereinbelow can be additionally employed as combinations or alone
in the applications of the gemini surfactants defined herein. These
surfactants can be used in quantities of from 0.1 to 99.9 wt %,
based on the total quantity of the different surfactants used in
the formulation. The non-limiting examples of non-ionic surfactants
given herein include fatty acid glycerides, fatty acid
polyglycerides, fatty acid esters, alkoxylates of higher alcohols,
alkoxylated fatty acid glycerides,
polyoxyethyleneoxypropyleneglycol fatty acid esters,
polyoxy-ethylene sorbitan fatty acid esters, polyoxyethylene-castor
oil derivatives or dehydrated castor oil is derivatives,
polyoxyethylene lanolin derivatives, polyoxy-ethylene fatty acid
amides, polyoxyethylene alkylamines, derivatives of alkanolamines,
alkylaminoxides, derivatives of protein hydrolysates, hydroxy mixed
ethers, alkylmono- or -polyglycosides and alkylglucamides (e.g.
N-methylalkyl-glucamides).
[0175] Examples of anionic surfactants, which are suitable for the
aforesaid combinations, include soaps, ethercarboxylic acids and
their salts, alkylsulfonates, .alpha.-olefin sulfonates,
.alpha.-sulfofatty acid derivatives (including those specified in
VVO 93/25646), dicarbonates (as defined in DE-A-196 22 612),
sulfonates of higher fatty acid esters, higher alcohol sulfates
(primary and secondary), alcohol ether sulfates, hydroxy mixed
ether sulfates, sulfates and carbonates of alkoxylated carboxylic
acid alkanol amides, salts of phosphate esters, taurides,
isethionates, linear alkyl benzene sulfonates, bridged alkyl
benzene sulfonates, i.e. dialkylmono- or -disulfonates of diphenyl
ethers, alkylarylsulfonates, sulfates of polyoxyethylene fatty acid
amides and derivatives of acylaminoacids, alkylethercarboxylic
acids, alkyl- and dialkylsulfosuccinates, alkenylsulfosuccinates,
alkyl- or alkenylsarcosinates, and sulfated glycerol
alkylethers.
[0176] Examples of cationic surfactants, which are suitable for the
aforesaid combinations, include alkyltrimethyl-ammonium salts,
dialkyldimethylammonium salts, alkyldi-methylbenzylammonium salts,
imidazolinium derivatives, alkylpyrdinium salts, quaternized fatty
acid esters of alkanolamines, alkylisoquinolinium salts,
benzethonium chlorides, and cationic acylaminoacid derivatives.
[0177] Examples of ampholytic and betainic surfactants, which are
suitable for the aforesaid combinations, include carbobetaines,
e.g. coco-acylamidopropyldimethylbetaine,
acylamidopentanediethylbetaine,
dimethylammoniohexanoate-acylamidopropane-(or -ethane-)dimethyl-(or
-diethyl-)-betaine, each with carbon chain lengths of from 10 to
18, sulfobetaines, imidazoline derivatives, soybean oil lipids, and
lecithin. The aforementioned amine-N-oxides can also be present in
polymeric form, wherein a ratio of amine to amine-N-oxide of from
10:1 to 1:1,000,000 and an average molecular mass of from 500 to
1,000,000, most preferably from 5,000 to 100,000 is required.
[0178] Examples of additional components, which can be employed
alone or as combinations with the surfactant compositions of the
invention, include carriers, hydrotropes, process auxiliaries,
dyestuffs or pigments, perfumes, solvents for liquid formulations
(most preferably alcohols with 1 to 6 carbon atoms and 1 to 6
hydroxy groups), solid fillers for bar soap formulations,
pearlescent agents (e.g. distearoyl glycerides), preservatives, or
buffers. If higher foaming power of a formulation is desirable,
e.g. when employed in body care products, C.sub.10- to
C.sub.16-alkanol amides can be added in quantities of from 1 to 10
wt %, referring to the total formulation. Moreover, additional
water-soluble magnesium salts can be added in quantities of from
0.1 to 2 wt % in order to enhance foaming and fat dissolving power.
Optionally, a few of the aforementioned surfactant compositions can
also be incorporated in the formulation after they have been
stabilized by adsorption on hydrophobic, porous substances and
sealed with another hydrophobic coat.
EXAMPLES
[0179] The following examples illustrate several embodiments of the
present invention.
Preparation of Emulsions
[0180] The micropigments utilized herein are titanium dioxide
coated with aluminium and glycerol ("UV Titan M 212" manufactured
by Kemira, Finland) and zinc oxide coated with dimethicone (INCI
nomenclature) ("Z-Cote HP 1" manufactured by Sun Smart, USA). For
comparison, commercially available emulsions are employed and
analyzed. TABLE-US-00003 Emulsion in water: "Tioveil AQ"
(manufacturer: Tioxide), approx. 40 wt % titanium dioxide dispersed
in water Emulsion in oil: "Tioveil MIG" (manufacturer: Tioxide),
approx. 40 wt % titanium dioxide dispersed in capric-/caprylic
triglyceride (e.g., "Miglyol 812" of CONDEA Chemie GmbH)
[0181] The particle size distribution was measured by laser light
scattering. The gemini surfactant mixtures of other surfactant
compositions of the subject invention showed similar
characteristics. They are included in the following tables as
particle wt %<1 .mu.m. TABLE-US-00004 Gemini Surfactant Variant
A (Formula) Structure A.A R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, (A.I)
X = Y =
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.ySO.sub.3Na,
wherein x = 14, y = 0 A.B R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, (A.I)
X = Y = (C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.yH,
wherein x = 14, y = 0 A.C R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, (A.I)
X = Y =
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.ySO.sub.3TIPA,
wherein x = 11, y = 0; TIPA = triisopropanol ammonium A.D R.sup.1 =
R.sup.3 = C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 =
C.sub.2H.sub.4, (A.I) X = Y =
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O--).sub.ySO.sub.3Na,
wherein x = 11, y = 0 A.E R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, (A.I)
X = Y =
(C.sub.2H.sub.4O--).sub.x(C.sub.3H.sub.6O).sub.yCH.sub.2CO.sub.2Na,
wherein x = 14, y = 0
[0182] TABLE-US-00005 Gemini Surfactant Variant B (Formula)
Structure B.A R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, A =
CH.sub.2, M = Na (B.I) B.B R.sup.5 = R.sup.6 =
C.sub.12H.sub.25/C.sub.14H.sub.29, X = C.sub.2H.sub.4, (B.II)
Y.sup.1 = CO.sub.2Na, Y.sup.2 =
--O--C(O)--C.sub.2H.sub.4--CO.sub.2Na B.C R.sup.5 = R.sup.6 =
C.sub.12H.sub.25/C.sub.14H.sub.29, X = C.sub.2H.sub.4, (B.II)
Y.sup.1 = CO.sub.2Na, Y.sup.2 =
--O--C(O)--C.sub.2H.sub.4--CO.sub.2Na B.D R.sup.1 = R.sup.3 =
C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.2 = C.sub.2H.sub.4, A =
C.sub.2H.sub.4, (B.III) FG = --SO.sub.3Na
[0183] TABLE-US-00006 Gemini Surfactant Variant C (Formula)
Structure C.A R.sup.1 = C.sub.11H.sub.23, B = C.sub.2H.sub.4,
R.sup.3 = CH.sub.2, R.sup.4 = C.sub.2H.sub.4, Y = COONa (C.I) C.B
R.sup.1 = C.sub.14H.sub.29, B = C.sub.2H.sub.4, R.sup.3 =
C.sub.2H.sub.4, R.sup.4 = C.sub.2H.sub.4, Y = COONa (C.I) C.C
R.sup.11 = C.sub.12 H.sub.25 --C(O)--C.sub.2H.sub.4--, A = N,
R.sup.12 = C.sub.2H.sub.4, (C.II) R.sup.4 = C.sub.2H.sub.4, Y = OH
C.D R.sup.21 = C.sub.11H.sub.23/C.sub.13H.sub.27, R.sup.22,
R.sup.23, R.sup.24 = C.sub.2H.sub.4 (C.V)
[0184] TABLE-US-00007 Gemini Surfactant Variant D (Formula)
Structure D.A R, R.sup.1 = --C.sub.11H.sub.23, R.sup.2 = --S--, X =
NZ, Z = --CH.sub.3, (D.I) Y, Y.sup.1 = glucosyl residue D.B R,
R.sup.1 = --C.sub.11H.sub.23, R.sup.2 = single bond, AO = --C(O)--,
(D.II) T, T.sup.1 = OM, M = Na D.C R, R.sup.1 = C.sub.12H.sub.24,
R.sup.8 = NYY1, Y = --CH.sub.3, Y.sup.1 = glucosyl (D.III) residue
D.D R.sup.5 = --C.sub.2H.sub.3.dbd., R = C.sub.12H.sub.24, R.sup.4
= C.sub.2H.sub.4, x = 3, T, T.sup.1 = H (D.IV)
Example 1
Preparation of Pigment Emulsions in Water
Batch Size: 100 g
[0185] The gemini surfactant and the co-amphiphile were dissolved
in water at 80.degree. C. until a slightly turbid, homogeneous
emulsion was obtained. After cooling of the aqueous surfactant
phase to approx. 30.degree. C., the pigment was dispersed in the
aqueous phase with stirring. The emulsion then was homogenized by
stirring for five minutes with an Ultra-Turrax stirrer running at
max. peripheral velocity. TABLE-US-00008 Components wt % (m/m)
Gemini surfactant 4.25 C.sub.8-C.sub.10 fatty alcohol 0.75 Water
45.00 Pigment 50.00
[0186] After 24 hours at room temperature, the particle size
distribution was measured. TABLE-US-00009 Gemini Median/Particle
Size Pigment Surfactant Distribution (.mu.m) Titanium dioxide A.A
0.37 (UV Titan M212, Kemira) A.B 0.33 A.C 0.38 A.D 0.37 A.E 0.36
Zinc oxide A.A 0.37 (Z-Cote HP 1, Sun Smart) A.B 0.37 A.C 0.38 A.D
0.37 A.E 0.39 Titanium dioxide B.A 0.38 (UV Titan M212, Kemira) B.B
0.33 C.A 0.37 C.B 0.36 D.A 0.37 D.B 0.34
Example 2
Preparation of Titanium Dioxide Emulsions in Oil
Batch Size: 100 g
[0187] The gemini surfactant and the co-surfactant were dissolved
in oil (Miglyol 812, CONDEA Chemie GmbH) at 80.degree. C. until a
slightly turbid, homogeneous emulsion was obtained. After cooling
of the surfactant phase to approx. 30.degree. C., the pigment was
admixed to the oil phase with stirring. The emulsion then was
homogenized by stirring for five minutes with an Ultra-Turrax
stirrer running at max. peripheral velocity. TABLE-US-00010
Components wt % (m/m) Gemini surfactant 6.00 Co-amphiphie, cetyl
alcohol 1.00 Miglyol .RTM. 812 58.00 UV Titan M212 35.00
[0188] After 24 hours at room temperature, the particle size
distribution was measured. TABLE-US-00011 Gemini Median/Particle
Size Pigment Surfactant Distribution (.mu.m) Titanium oxide A.A
0.45 (UV Titan M212, Kemira) A.B 0.37 A.C 0.44 A.D 0.42 A.E 0.38
B.A 0.45 B.B 0.37 C.A 0.44 C.D 0.43 D.A 0.44 D.D 0.43
Example 3
Preparation of Zinc Oxide Emulsions in Oil
Batch Size: 100 g
[0189] The gemini surfactant and the co-amphiphile were dissolved
in oil (Miglyol.RTM. 812, CONDEA Chemie GmbH) at 80.degree. C.
until a slightly turbid, homogeneous emulsion was obtained. After
cooling of the surfactant phase to approx. 30.degree. C., the
pigment was admixed to the oil phase with stirring. The emulsion
then was homogenized by stirring for five minutes with an
Ultra-Turrax stirrer running at max. peripheral velocity.
TABLE-US-00012 Components wt % (m/m) Gemini surfactant 4.50
Co-amphiphie, cetyl alcohol 0.80 Miglyol 812 44.70 Z-Cote HP 1
50.00
[0190] After 24 hours at room temperature, the particle size
distribution was measured. TABLE-US-00013 Variant A Gemini
Median/Particle Size Pigment Surfactant Distribution (.mu.m) Zinc
oxide A.A 0.41 (Z-Cote HP 1, Sun Smart) A.B 0.37 A.C 0.41 A.D 0.40
A.E 0.45 B.A 0.41 B.D 0.40 C.A 0.42 C.B 0.38 D.A 0.42 D.B 0.38
Example 4
[0191] A combination of gemini surfactant, glyceryl stearate,
glyceryl stearate citrate, and fatty alcohol was employed as a
complex emulsifier: TABLE-US-00014 Complex Emulsifier A.A [wt %]
Gemini surfactant A.A 10.00 Glycerolmono- 35.00 distearate Behenyl
alcohol 40.00 Glyceryl stearate citrate 15.00
[0192] TABLE-US-00015 Formulation [wt %] Complex emulsifier 1.90
A.A Miglyol 812 63.10 UV Titan M212 35.00
Procedure [0193] Dissolve emulsifier in oil at 80.degree. C.,
[0194] allow to cool to 30.degree. C. [0195] Slowly admix pigment,
[0196] then disperse for 15 minutes at 1,500 rpm
[0197] Analytical Results (PSA=Particle Size Analysis)
TABLE-US-00016 D-3-2/0 Tioveil Fin PSA Median [.mu.m] 0.35 0.33
<1 .mu.m [%] 96.5 92.0 Median [.mu.m] 0.34 0.35 <1 .mu.m [%]
96.4 91.6 Rheology Flow point [mPa] 5,000 not determined Viscosity
(at 1 s.sup.-1) [mPas] 31,200 not determined
Example 5
[0198] The following formulation allowed to disperse a
hydrophobically coated zinc oxide. TABLE-US-00017 Formulation [wt
%] Complex emulsifier A.A 2.0 Miglyol 812 47.70 Z-Cote HP 1
50.00
[0199] Procedure [0200] Dissolve emulsifier in oil at 80.degree.
C., allow to cool to 30.degree. C. [0201] Slowly admix pigment,
then disperse for 15 minutes at 1,500 rpm
[0202] This system, too, proved that the complex emulsifier is an
efficient dispersant in oil:
[0203] Analytical Results (PSA=Particle Size Analysis)
TABLE-US-00018 D-3-4/0 PSA Median [.mu.m] 0.38 <1 .mu.m [%] 84.0
Median [.mu.m] 0.38 <1 .mu.m [%] 86.1 Rheology Flow point [mPa]
14,100 Viscosity (at 1 s.sup.-1) [mPas] 39,200
Emulsions
Example 6
Comparative Example
[0204] TABLE-US-00019 Conventional Preparation of O/W Emulsions
Brand Manufacturer CTFA/INCI Nomenclature wt % Phase A Tego Care
450 Th. Polyglyceryl-3 methyl 5.00 Goldschmidt glucose distearate
Alternative: Gemini surfactant Condea Cetyl alcohol 4.00 A.F or
B.C, each Henkel 1.00 plus Lanette 16 Miglyol 812 N CONDEA
Caprylic/capric triglyceride 6.00 Crodamol OP Croda 2-Ethylhexyl
palmitate 2.00 Eutanol G Henkel Octyldodecanol 2.00 Softisan 100
CONDEA Hydrogenated 3.00 coco-clycerides Phase B Pricerina 9091
Unichema Glycerol 3.00 Demin. Wasser Aqua 78.50 Phase C Phenonip
Nipa Phenoxyethanol 0.50 methylparabene, propylparabene,
butylparabene Total 100.00 Legend: Gemini A.F: R.sup.1 = R.sup.3 =
C.sub.11H.sub.23--/C.sub.13H.sub.27-1 R.sup.2 = C.sub.2H.sub.4, X =
Y = (C.sub.2H.sub.40--).sub.x(C.sub.3H.sub.6O--).sub.y; SO.sub.3Na,
wherein x = 17, y = 0 (A.I)
Preparation of Emulsion by Conventional Method: [0205] Heat phases
A and B separately to 75.degree. C. [0206] Admix phase A to phase B
at 75.degree. C. and homogenize for 1 minute at 75.degree. C.
[0207] Cool the emulsion to room temperature with gentle
stirring
[0208] The O/W emulsion prepared with Tego Care 450 had a viscosity
of 20,600 mPa s (shear rate 1 s.sup.-1, 25.degree. C.) and an
average droplet size in the range from 2 to 6 .mu.m.
[0209] The O/W emulsion prepared with gemini A.F and cetyl alcohol
had a viscosity of s<1,000 mPas (shear rate 1 s.sup.-1,
25.degree. C.). The droplet size was unsatisfactory. The O/W
emulsion prepared with gemini B.C and cetyl alcohol had a viscosity
of only <1,300 mPas (shear rate 1 s.sup.-1, 25.degree. C.).
Example 7
Preparation of O/W Emulsions According to the PTT Method of the
Subject Invention
[0210] TABLE-US-00020 Brand Manufacturer CTFA/INCI Nomenclature wt
% Phase A Tego Care 450 Th. Polyglyceryl-3 methylglucose 5.00
Goldschmidt distearate Alternative: Gemini A.F or CONDEA Cetyl
alcohol 4.00 B.C Henkel 1.00 plus Lanette 16 Miglyol 812 N CONDEA
Caprylic/capric triglyceride 10.00 Phase B Pricerina 9091 Unichema
Glycerol 1.50 Demin. water Aquar 18.50 Phase C Pricerina 9091
Unichema Glycerin 1.50 Demin. water 60.00 Phase D Phenonip Nipa
Phenoxyethanol 0.50 methylparabene, propylparabene, butylparabene
Total 100.00 Legend: Gemini A.F: R.sup.1 = R.sup.3 =
C.sub.11H.sub.23--/C.sub.13H.sub.27-1 R.sup.2 = C.sub.2H.sub.4, X =
Y = (C.sub.2H.sub.40--).sub.x(C.sub.3H.sub.6O--).sub.y; SO.sub.3Na,
wherein x = 17, y = 0 (A.I)
Preparation of the Emulsion According to the PTT Method
[0211] Phase A was heated to 60.degree. C. Phase B was separately
heated to 50.degree. C. Phase A then was slowly admixed to phase B
with considerable homogenization. Homogenization was performed for
1 minute. Phases C and D then were admixed with gentle stirring to
give a homogeneous product.
[0212] The O/W emulsion prepared with Tego Care.RTM. 450 had a
vis-cosity of 20,000 mPa (shear rate 1 s.sup.-1, 25.degree. C.) and
an average droplet size in the range from 2 to 6 .mu.m. This
emulsion is depicted in FIG. 1 (1,100 fold magnification, Normarski
interference prisma, viscosity 20,00 mPas, shear rate 1 s.sup.-1,
25.degree. C.). The average droplet size was in the range from 2 to
6 .mu.m.
[0213] The O/W emulsion prepared with gemini A.F and cetyl alcohol
is depicted in FIG. 2 (1,100 fold magnification, Normarski
interference prisma, viscosity 18,000 mPas, shear rate 1 s.sup.-1,
25.degree. C.). The O/W emulsion prepared with gemini B.C and cetyl
alcohol had a viscosity of 18,000 mPas (shear rate 1 s.sup.-1,
25.degree. C.). The droplet size was <<1 .mu.m.
[0214] The figures demonstrate that the emulsions prepared by the
PTT method using the surfactant compositions of the subject
invention are distinctly superior to conventional O/W emulsions
with respect to fineness and are at least equal regarding rheology.
Hence, when using the surfactant compositions of the invention, it
is possible to produce nanoemulsions under gentle conditions and
with moderate technical expenditure. Furthermore, emulsions
produced with the surfactant compositions of the invention impart a
silky touch.
Example 8
Test for Skin Irritation of Human Beings
Modified Duhring Chamber Test
[0215] The formulations defined hereinbelow were prepared according
to the aforementioned PTT method and were dermatologically
evaluated according to the method described by Frosch and Kligman
(P. J. Frosch, A. M. Kligman, The Duhring Chamber, Contact
Dermatitis, 5 (1979) 73-81; P. J. Frosch, A. M. Kligman, The soap
chamber test, J. Am. Acad. Dermatol., 1 (1979) 35-41).
TABLE-US-00021 Model Formulations for the Duhring Chamber Test
Formulation No. Brand 0-1 0-2 0-3 0-4 Phase A Tegin M 3.00 3.00
3.00 3.00 Gemini A.F 1.00 0.00 0.00 0.00 Gemini A.B 0.00 0.00 0.00
1.00 Emulgin B1 0.00 0.00 0.50 0.00 Emulgin B2 0.00 0.00 0.50 0.00
Emulgade PL1618 0.00 2.00 0.00 0.00 Lanette O 1.50 0.50 1.50 1.50
Phase B Cetiol V 9.00 9.00 9.00 9.00 Cetiol SN 9.00 9.00 9.00 9.00
Phase C Water 23.50 23.50 23.50 23.50 Glycerol 1.50 1.50 1.50 1.50
Phase D Water 47.35 47.35 47.35 47.35 Glycerol 1.50 1.50 1.50 1.50
Phase D1 Keltrol 0.15 0.15 0.15 0.15 Phase E Total 100.00 100.00
100.00 100.00
[0216] To marked spots on the volar surface of the forearm there
was applied 0.05 ml of product using aluminum chambers (Finn
Chambers, 12 mm in diameter) containing adequate filter papers. The
application schedule was as follows: TABLE-US-00022 1st day 18 h
application - 6 h pause 2nd, 3rd, 4th, 5.sup.th, and 6th day 6 h
application - 18 h pause 7th day Pause 8th day Evaluation
[0217] For comparison, water was employed as a non-irritating
substance and sodium lauryl sulfate (0.2%) was chosen as an
irritating agent. Three methods were employed for the evaluation:
visual (in five steps), chromametry, and measurement of the
transepidermal dehydration as an indicator of barrier damage. The
ratings of the test substances were non-irritating, moderately
irritating, fairly irritating, and strongly irritating.
[0218] Each of the four test products was found to be
nonirritating, both regarding the degree of redness and the
transepidermal dehydration, Statistically, no significant
differences were found between the products. In contrast thereto,
sodium lauryl sulfate produced the irritating effects as expected,
thus confirming suitability and correct procedure of the test
method.
* * * * *