Note: Descriptions are shown in the official language in which they were submitted.
2 1 9~067
POLYGLYCERIN EST~R SULFOSUCCINATES,
METHOD FOR THEIR PREPARATION, AND THEIR USE
The objects of the invention are new polyglycerin fatty acid
ester sulfosuccinates, a method for their preparation, and their
use as cleaning agents and for cosmetic preparations.
Cosmetic preparations, particularly those used in the hair
and body cleansing field, such as shower gel, foam baths, hair
shampoos, hair care agents, and liquid soaps, contain primarily
anionic surfactants such as carboxylates, alkyl sulfates, alkyl
ether sulfates, and sulfosuccinates as cleaning components.
These preparations are intended to clean the surface of the
skin, preferably with only the film that is attached to it, and
can consist of bodily excretions such as sweat and fats,
dandruff, and deposited dirt from the environment. The cleaning
agents should in no way leach the skin, irritate it, or have a
detrimental effect on its natural function.
Since these preparations can lead to irritations of the skin
if used frequently--in the last few years--so-called mild
surfactants are also frequently used--such as betaines, protein
derivatives, ampholytes, alkyl ether carboxylates, and
sulfosuccinates--to improve the skin and ocular mucosal
tolerability.
In particular for baby care agents, baby shampoos, and hair
care agents in the form of, for example, hair care emulsions,
hair rinses, hair treatments, hair dryer lotions, and aerosol
foams, particular value is attached to extremely low contents of
substances that irritate the skin and ocular mucosa. The anionic
2199067
surfactants that are conventionally used because of their
excellent cleaning and foam formation properties can have their
irritation effect considerably reduced by means of the known mild
cosurfactants, but in practice improvements are still required,
particularly insofar as the ocular mucosal tolerability is
concerned.
At high concentrations or alone, the mild surfactants are
largely irritation free, but in that case their foaming and
cleaning properties do not meet the practical requirements and
they present unsatisfactory viscosities.
- Because of the increased environmental awareness, products
continue to be requested which are based on natural renewable raw
materials that present no toxicity and that can be degraded
rapidly and completely in communal clarification installations
without toxic intermediates.
The products that have been introduced in practice, such as
mono- and/or difatty acid esters and their alkoxylates based on
glycerin or polyglycerin, present lower toxicities and they are
mild, non-skin-irritating, but they do not meet the practical
requirements insofar as their cleaning effect and solubility are
concerned.
The task of the p~esent invention is to overcome these
drawbacks of the state of the art and to make available mild,
skin-friendly cleaning agents for household and industrial use
and for cosmetic preparations, particularly those used in the
hair and body cleansing field.
This task is solved by the combined use, according to the
invention, of fatty acid ester sulfosuccinates based on
polyglycerins.
21 99067
The focus of the invention includes fatty acid ester
sulfosuccinates of general formula 1
~ ~ (E~)b-~-~-CH2-IH-CH2-~-]a-CH2-CH-CH2-o-(EO)c_~
o-(Eo)d-R3 1-(Eo)e-R4
with the meanings
Rl = FS-CO, where FS is a C~21 hydrocarbon residue that
optionally contains multiple bonds and/or is optionally
substituted with one or more OH groups
R2 = Rl or -CO-CH(SO3-X+)-CH2-COO-X+ or
-CO-CH2-CH(SO3-X+)-COO-X+
R3, R4 = the same or different = H, Rl, R2,
EO = the residue -CH2-CH2-O- with a, b, c, d, e = 0-5
X+ = H+ or a cation, prepared by the esterification of
polygLycerins in the first step with fatty acids FS-COOH,
followed by the addition of maleic acid anhydride in the second
step and sulfonation and optionally partial or complete
neutralization of the reaction product with one or more organic
andtor mineral bases.
Another object of the invention is a method for the
preparation of compounds of general formula 1.
Other objects of the invention are aqueous skin and hair
care agents as well as skin and hair cleaning agents in the form
of, for example, hair care emulsions, hair rinses, hair
treatments, hair dryer lotions, and aerosol foams; rinsing
agents, all-purpose cleaners, neutral cleaners, hair care, and
21 99067
cleaning agents, which are characterized in that they contain 1-
40, preferably 2-30, parts by weight of at least one of the
compounds of general formula (1), along with defined quantities
of at least one surfactant from the group of nonionic,
amphoteric, zwitterionic, and ionic surfactants, preferably 0.1-
40 parts by weight, optionally 0.1-15 parts by weight, of one of
the conventional agents from the group of additives and auxiliary
substances, thickeners, scents, preservation agents, dyes, plant
extracts and optionally water up to 100 [parts].
Other objects of the invention are characterized by the
claims.
The starting substance for the preparation of the compounds
according to the invention of general formula (1) is polyglycerin
of the formula HO-[CH2-CH(OH)-CH2-O-]a-CH2-CH(OH)-CH2-OH. The
polyglycerins that are used according to the invention are
commercial industrial products that can be manufactured by
methods that in themselves are known, such as base-catalyzed
polycondensation of glycerin (Ullmanns Encyklopadie der
techni-schen Chemie [Ullmann's Encyclopedia of Industrial
Chemistry], Vol. A 12, 4th edition, Verlag Chemie, Weinheim,
1989, pp. 477 ff; US-PS-2605293 (1952), Shell Development Co.;
US-PS-2810768 (1957) Shell Development Co.; DE-3600388 (Solvay),
1986; DE-3410520 (Solvay), 1984). Depending on the manufacturing
method, these industrial products have different oligomerization
degrees and distributions.
These polyglycerins can be reacted in the first step with 1
or 2 mol of fatty acids or their esters using the known methods
to form the ester (G. Jakobson, Fette, Seifen, Anstrichmittel,
Vol. 88 (1986), pp. 101-105). Monoesters are preferred according
to the invention.
2 1 99067
s
As acids, the monofunctional fatty acids or fatty acid
mixtures with 8-22 C atoms are used--preferably naturally
occurring ones such as coconut fatty acids, palm kernel fatty
acids, palm fatty acids, and talc fatty acids.
According to the invention, it is preferred to use monobasic
acids with 8-18 C atoms such as oleic acid, linoleic acid,
linonlenic acid, ricinoleic acid, coconut fatty acid, or mixtures
thereof.
These esters are reacted--in the second step using a method
that in itself is known (J. Am. Oil Chemist's Soc., 1956, Vol.
33, p. 517, E-A-0-334482)--with alkylene oxides-such as,
particularly, ethylene oxide, to make the polyglycol ether
esters, during which step 0-5 mol of alkylene oxide is added as a
statistically mean value per hydroxyl group.
The polyglycerins can also be alkoxylated in the first step
according to the above-indicated methods and in the second step
they can be reacted with 1 or 2 mol of fatty acid to make the
fatty acid ester.
The reaction to make the sulfosuccinate is carried out with
maleic acid anhydride and subsequent sulfonation with sodium
sulfite according to methods that in themselves are known (DE-OS-
2700072).
For each mole of hydroxyl group to be reacted, a maximum of
1 mol of maleic acid anhydride is stirred at 60-80~C until the
reaction of the anhydride is completed. The maleic acid semiester
is subsequently introduced into an aqueous sodium sulfite
solution (1 equivalent of sulfite per equivalent of semiester)
and sulfonated at 60-80~C, until all the sulfite has reacted. The
pH of the aqueous product is then adjusted to neutral.
21 ~9067
In general, the method is carried out according to the
invention in such a manner that in the first step the
polyglycerin is esterified with the fatty acid(s), optionally
with the combined use of an esterification catalyst, at 180-210~C
with removal of the reaction water, with the ester then being
optionally reacted in the second step in the presence of a basic
catalyst at 80-150~C and 1-10 bar with an alkylene oxide to form
an alkyloxylate, which is then reacted by the addition of maleic
acid anhydride at 60-80~C to form the semiester and, in the last
step at 60-80~C is reacted with an aqueous sodium sulfite
solution to make the salt of the corresponding sulfonic acid.
The compounds according to the invention are represented in
idealized form by general formula tl). The industrial mixtures
contain, besides the indicated monofatty acid esters or difatty
acid esters, also portions of the starting products, and the
indicated alkoxylation degrees are statistical means.
~ or the use according to the invention, cleaning is not
necessary, that is, the industrial mixtures can be further used
directly as they are.
The mixtures according to the invention for cleaning
purposes and cosmetics are generally in the form of aqueous
agents or aqueous alcohol solutions, creams, emulsions, or gels;
they also can contain, as an adaptation to the intended
application, the usual auxiliary substances and additives in each
case, which are conventionally used for the preparation of
cleaning agents and cosmetic preparations in the hair and body
cleaning field and also hair and body care, that is, for shower
gels, foam baths, shampoos, liquid soaps, baby care and washing
agents, hair lotions and hair rinses, and conditioning shampoos,
- 2 1 ~9067
as well as for mild cleaning agents such as dishwashing agents,
all-purpose cleaners, or neutral cleaners for manual use.
For cosmetic applications, the surfactants, scents,
preservation agents, dyes, plant extracts or other cosmetic
additives that are standard in these fields can also be used in
combinations.
As surfactants it is possible to use, besides the known
betaines, amphoteric, and nonionic compounds for the cleaning
formulations, particularly the anionic surfactants such as
carboxylates, alkyl sulfates, alkyl ether sulfates,
alkylsulfonates, and alkyl ether sulfonates, alkyl
sulfosuccinates. According to the invention, it is preferred to
use alkylamidobetaines such as REWOTERIC~ 1) AM B 13 and AM B 14,
as well as AM 8 45, carboxyglycinates such as REWOTERIC~ AM 2 C
NM, carboxypropionates such as REWOTERIC~ AM KSF 40,
sulfobetaines such as REWOTERIC~ AM CAS, anionic surfactants such
as ether sulfates REWOPOL~ 2) NL 2, ether carboxylates such as
REWOPOL~ RLN 100, sulfosuccinates such as REWOPOL~ SB FA 30,
REWOPOL~ SBZ, REWODERM~ 3~ SPS, nonionic surfactants such as
glycerin fatty acid ester ethoxylates such as REWODERM~ ES 90,
glycerin monostearates such as REWOMUL~ 4~ MG, cetyl alcohol, and
cationic surfactants such as REWOQUAT WE 18, REWOQUAT WE 28, or
REWOQUAT WE 38 DPG;
(1), 2), 3), 4) = trademarks of the company REWO Chemische
Werke GmbH, Steinau an der Stra~e).
Besides the compounds according to the invention, which are
used in quantities of 1-40 parts by weight, particularly 2-30
parts by weight, in shampoos and 1-7 pa~ts by weight, preferably
1-5 parts by weight, in creams and 1-10, preferably 1.5-8, parts
by weight [sic; no product name given], and in quantities of 0.5-
21 99067
25 parts by weight, preferably O.S-15 parts by weight, in hair
care agents, in cleaning agents, the other surfactants in
shampoos are normally used in quantities of 1-40 parts by weight,
preferably 2-30 parts by weight, and in creams in quantities of
1-10 parts by weight, preferably 2-8 parts by weight.
As thickeners, 0.1-10 parts by weight of the compounds
normally used in this field is used, such as glycerin fatty acid
ester ethoxylates, fatty alcohol ethoxylates, fatty acid
alkylolamides, and the usual alkali, alkaline earth, and ammonium
salts, which at 20~C are soluble in quantities of at least 1 wt%
in water, such as NaCl and NH4Cl. Thickeners are substances or
compounds that are used to increase the viscosities of mixtures
or formulations.
The analysis values indicated in the following examples are
determined according to the methods that are normally used in
this field:
Acid number (SZ)
The acid number is a measure of the content of free acids in
fats or technical-grade fatty acids, and it indicates the amount
of potassium hydroxide needed, in mg, to neutralize 1 g of
substance.
The values are determined according to the DGF unit method
C-V4.
Dry matter content
This content is determined by heating and drying at 105~C
until the weight is constant.
2 1 99067
Hydroxy number (OHZ)
The hydroxy number is used to determine the content of
hydroxyl groups; it indicates the number of milligrams of
potassium hydroxide needed to neutralize 1 g of fat in the
acetylation of used acetic acid (mg KOH/g).
Benzavlon-WAS
The content of detergent substance (B-WAS) indicated in the
following examples is obtained by titration using the
conventional two-phase titration with benzalkonium chloride
(Benzavlon) against methylene blue as the indicator (see also S.
R. Epton, Nature (London), Vol. 160, 1967, p. 795).
Examples
1. Synthesis of polyglycerin esters
Example 1.1
Ester from triglycerin (Solvay) and HK 12-18 fatty acid
254.2 g (1.1 mol) of triglycerin, 233.1 g (1.1 mol) of fatty
acid HK 12-18, and 1.0 g (0.4%) of hypophosphoric acid are
combined in a reaction vessel equipped with a thermometer,
stirrer, cooler, and water separator, then heated under a
nitrogen atmosphere to 190~C, and the reaction water produced~is
removed by distillation. A vacuum (approximately 50 mbar) is
21 99067
applied when the [reaction3 temperature is reached, and the rest
of the reaction water is removed. When an acid number of
approximately 5 mg KOH/mg is reached, the reaction is allowed to
continue for 1 h at 180~C, followed by cooling.
The reaction product presented the following analytical
data:
VZ 135.2 mg KOHtg
OHZ 344.0 mg KOH/g
SZ 2.5 mg KOH/g
Example 1.2
Ester from triglycerin (Solvay) and C 12 fatty acid
331.7 g (1.4 mol) of triglycerin, 277 g (1.4 mol) of C 12
fatty acid, and 2.4 g of hypophosphoric acid are combined in a
reaction vessel equipped with a thermometer, stirrer, cooler, and
water-separator, then heated under a nitrogen atmosphere to
205~C, and the reaction water is removed by distillation. A
vacuum (approximately 50 mbar) is applied when the temperature is
reached, and the rest of the reaction water is removed. When an
acid number of approximately 5 mg KOH/mg is reached, the reaction
is allowed to continue for 1 h at 180~C, followed by cooling. The
reaction product presented the following analytical data:
VZ 129.6 mg KOH/g
OHZ 516.2 mg KOH/g
SZ 4.5 mg KOH/g
21 99067 11
Example 1.3
Ester from C 12 fatty acid and polyglycerin T ~commercial
product of the Solvay company; a in the general formula (1) =
2-6)
295 g (0.9 mol) of triglycerin, 188 g (0.9 mol) of C 12
fatty acid HK, and 0.9 g of hypophosphoric acid are combined in a
reaction vessel equipped with a thermometer, stirrer, cooler, and
water separator, then heated under a nitrogen atmosphere to
200~C, and the reaction water produced is removed by
distillation. A vacuum (approximately 50 mbar) is applied when
the ~reaction3 temperature is reached, and residues of the
reaction water are removed at 180~C. When an acid number of
approximately 5 mg KOH/mg is reached, the reaction is allowed to
continue for l h at 180~C, followed by cooling.
The reaction product presented the following analytical
data: -
VZ 119.2 mg KOH/g
OHZ 403.1 mg KOH/g
SZ 1.2 mg KOH/g
Example 1.4
Ester from polyglycerin T (Solvay) and C 8-18 fatty acid
786 g (2.5 mol) of polyglycerin, 733.6 g (3.75 mol) of C 8-
18 fatty acid, and 5.0 g of hypophosphoric acid are combined in a
2 1 99067
12
reaction vessel equipped with a thermometer, stirrer, cooler, and
water separator, then heated under a nitrogen atmosphere to
205~C, and the resulting reaction water is removed by
distillation. A vacuum (approximately 20 mbar) is applied when
the temperature is reached, and the rest of the reaction water is
removed. When an acid number of approximately 5 mg KOH/mg is
reached, the reaction is allowed to continue for 1 h at 180~C,
followed by cooling. The reaction product presented the following
analytical data:
VZ 149.6 mg KOH/g
OHZ 409.0 mg KOH/g
SZ 4.9 mg KOH/g
2. Ethoxylation
Example 2.1
490.3 g (0.73 mol) of the polyglycerin ester from Example
1.4 are reacted in such a manner, after the addition of 2.8 g of
KOH (100%) at approximately 140~C in the laboratory autoclave in
portions with a total of 310 g (7.0 mol) of ethylene oxide, that
the maximum pressure was 5 bar.
Analytical data:
VZ 136.3 mg KOH/g
OHZ 234 mg KOH/g
- 2 1 99067 13
Example 2.2
620.8 g (1.2 mol) of the polyglycerin ester from Example 1.4
are reacted in such a manner, after the addition of 1.9 g of KOH
(100%) at approximately 140~C in the laboratory autoclave in
portions with a total of 533 g (12.1 mol) of ethylene oxide, that
the maximum pressure was 5 bar.
Analytical data:
VZ 95.7 mg KOH/g
OHZ 160.4 mg KOH~g
3. Semiester formation and sulfonation
Example 3.1
489 g (0.5 mol) of the polyglycerin ester ethoxylate from
Example 2.2 are reacted at 70-80~C under N2 with 50.2 g (0.S mol)
of mal-eic acid anhydride and reacted for ~ h at this temperature.
The product so obtained is slowly added dropwise to a solution of
49.7 g (0.25 mol) of sodium bisulfite in 580 g of water at 80-
85~C. The solution, after adjustment, presented the following
analytical data:
Dry residue 49.6%
Benzavlon-WAS 32.3%
pH (5ff) 6.3
2 1 9~067
14
Example 3.2
489 g (0.5 mol) of the polyglycerin ester ethoxylate from
Example 2.2 are reacted at 70-80~C under N2 with 87.9 g
~0.88 mol3 of maleic acid anhydride and reacted for 3 h at this
temperature. The product so obtained is slowly added dropwise to
a solution of 87.0 g (0.44 mol) of sodium bisulfite in 1000 g of
water at 80-85~C. The solution, after adjustment, presented the
following analytical data:
Dry residue 50.2%
Benzavlon-WAS 43.7%
pH (5%J 6.2
Example 3.3
389 g (0.75 mol) of the polyglycerin ester from Example 1.1
are reacted at 70-80~C under N2 with 92.5 g (0.94 mol) of maleic
acid anhydride and reacted for 2 h at this temperature.
The product so obtained is slowly added dropwise to a
solution of 91.6 g (0.47 mol) of sodium bisulfite in 570 g of
water at 80-85~C. The solution, after adjustment, presented the
following analytical data:
Dry residue 39.2%
Benzavlon-WAS 28.7%
pH (5%) 6.1
21 99067
Example 3.4
427 g (0.8 mol) of the polyglycerin ester from Example 1.1
were reacted at 70-80~C under N2 with 122 g (1.2 mol) of maleic
acid anhydride and reacted for 2 h at this temperature.
The product so obtained is slowly added dropwise to a
solution of 121 g (0.6 mol) of sodium bisulfite in 1000 g of
water at 80-85~C. The solution, after adjustment, presented the
following analytical data:
Dry residue 40.7%
Benzavlon-WAS 36.0%
pH (5%) 5.9
Example 3.5
427 g (0.8 mol) of the polyglycerin ester from Example 1.4
are reacted at 70-80~C under N2 with 126 g (1.2 mol) of maleic
acid anhydride and reacted for 4 h at this temperature.
The product so obtained was slowly added dropwise to a
solution of 125 g (0.6 mol) of sodium bisulfite in 1000 g of
water at 80-85~C. The solution, after adjustment, presented the
following analytical data:
Dry residue 48.3%
Benzavlon-WAS 48.0%
pH (5%) 5.4
2 1 99067
16
Example 3.6
* = Trademark of the company REWO Chemie Werke GmbH, Steinau
an der Stra~e
943 g (1.1 mol) of triglycerin laurate are reacted at 70-
80~C under N2 with 182 g (1.9 mol) of maleic acid anhydride and
reacted for 2 h at this temperature.
The product so obtained is slowly added dropwise to a
solution of 165 g (0.9 mol) of sodium bisulfite in 1000 g of
water at 80-85~C. The solution, after adjustment, presented the
following analytical data:
Dry residue 50.6%
Benzavlon-WAS 49.6%
pH (5%) 5.7
Basic formula: Skin cleaning agent and makeup remover for
sensitive skin
Compound according to the invention 2-8 parts by weight
REWOTERIC~* AM B 14 2-8 parts by weight
Hydroxyethylcellulose 0.2-1.5 parts by
weight
Demineralized water up to 100
2 1 ~0~7
17
Basic formula: Skin cream
Compound according to the invention 1-5 parts by weight
Glycerin monodistearate 2-10 parts by weight
Cetyl alcohol 1-4 parts by weight
Paraffin oil 3.5~E 4-12 parts by weight
Glycerin 1-5 parts by weight
Preservation agent 0-3 parts by weight
~emineralized water up to 100
Basic formula: Mild baby shampoo
Compound according to the invention 10-40 parts by
weight
REWOTERIC~* AM B 45 5-25 parts by weight
REWODERM~* LI S 80 1-10 parts by weight
NaCl 0.5-4 parts by
weight
Demineralized water . up to 100
Basic formula: Rinsing agent
Compound according to the invention 1-10 parts by weight
REWOPOL~* NL 3-28 1-30 parts' by weight
REWOTERIC~ AM CAS ~ 0-5 parts by weight
REWOPOL~* LA 6 0-10 parts by weight
- 21 99067
18
Basic formula: Mild shower gel
Compound according to the invention 2-15 parts by weight
REWOTERIC~* AM G 30 5-25 parts by weight
REWOTERIC~* AM CAS 0-4 parts by weight
REWOQUAT~* RTM 50 0-3 parts by weight
REWODERM~* LI 48-50 1-10 parts by weight
Demineralized water up to 100
Basic formula: Hair shampoo
Compound according to the invention 2-8 parts by weight
REWOPOL~* NL 2-28 4-10 parts by weight
REWOTERIC~ AM B 13 2-8 parts by weight
REWODERM~* LI 420-70 1-4 parts by weight
Demineralized water up to 100
Basic recipe: Baby shampoo
.
Compound according to the invention 2-8 parts by weight
REWOTERIC~* AM 2 C NM 2-8 parts by weight
REWOTERIC~* AM B 13 4-12 parts by weight
REWOPOL~ NL 2-28 2-10 parts by weight
REWODERM~* LI 48-50 1-4 parts by weight
Demineralized water up to 100
21 99067
Basic recipe: Hair rinse
Compound according to the invention 0.5-15 parts by
weight
REWOQUAT~* WE 18 or
REWOQUAT~* WE 28 or REWOQUAT~*
WE 38 DPG - 1-15 part by weight
Citric acid 0-3 parts by weight
REWOPOL~* SB FA 30 0.5-10 parts by
weight
Demineralized water up to 100
Basic formula: Shampoo 2 in 1 ultramild
Compound according to the invention 0.5-15 parts by
weight
REWOQUAT~* CPEM 1-15 parts by weight
REWOPOL~* NL 2-28 5-45 parts by weight
REWOTERIC~* AM B 50 - 2-15 parts by weight
REWODERM~* LI S 80 0.5-10 parts by
weight
Citric acid 0-3 parts by weight
REWOPOL~* SB FA 30 0.5-10 parts by
weight
Preservation agent 0-3 parts by weight
Demineralized water up to 100
21 ~9067
Cosmetic formulations
The following formulations can be prepared by simply
stirring the formula components in water. All formulas are
indicated in wt% calculated with respect to the solid matter.
Explanation of the INCI names of the surfactants used
REWOMUL~ MG Glyceryl stearate
REWOPOL~ SB FA 30 Disodium laureth sulfosuccinate
~EWOTERIC~ AM B 45 Cocamidopropylbetaine
REWOTERIC~ AM B 13 Cocamidopropylbetaine
REWOTERIC~ AM B 14 Cocamidopropylbetaine
REWOTERIC~ AM 2 C NM Disodium cocoamphodiacetate
REWOPOL~ SBZ Disodium PEG-4 cocoamido MIPA-
sulfosuccinate
REWODERM~ ES 90 PEG-7 glycerin cocoate
REWODERM~ LI S 80 PEG-200 hydrogenated glyceryl
- palmitate (and) PEG-7 glyceryl
cocoate
REWOPOL~ NL 2-28 Sodium laureth sulfate
REWOTERIC~ AM G 30 Disodium lauroamphodiacetate (and)
sodium lauryl sulfate (and)
hexylene glycol
REWODERM~ LI 48-50 PEG-80 glyceryl tallowate
REWODERM~ LI 420 PEG-200 glyceryl tallowate
REWODERM~ LI 420-70 PEG-200 glyceryl tallowate mod.
REWOTERIC~ AM CAS Cocoamidopropyl hydroxysultaine
REWOPAL~ LA 6 Laureth-6
21 9~067
. 21
REWOQUAT~ RTM 50 Ricinoleamidopropyltrimonium
methosulfate
REWOQUAT~ WE 18 Dihydrogenated tallow hydroxyethyl
monium methosulfate
REWOQUAT~ WE 28 Dihydrogenated palmoylethyl
hydroxyethylmonium methosulfate
REWOQUAT~ WE 38 DPG Dihydrogenated palmoylethyl
hydroxyethylmnoium methosulfate
REWOQUAT~ CPEM PEG-5 cocomonium methosulfate
Analytical methods
Calcium hardness tolerability: DIN 53 905
Skin tolerability: RBC test; W. J. W. Pape, U.
Pfannenbecker, and U. Hoppe, Mol. Toxicol., 1987, Vol. 1, p. 525.
Evaluation:
L/D value Ranking
>100 Not irritating
>10 Slightly irritating
>1 Moderately irritating
>0.1 Irritating
<0.1 Strongly irritating
Surface tension: Dr. R. Hensch; Fette, Seifen,
Anstrichmittel, 1970, Vol. 72, p. 969
21 99067
22
Viscosity: Brookfield rotation viscosimeter (beaker and
spindle) measured at 20~C according to the instructions of the
apparatus manufacturer)
Foaming capacity: According to Ross-Miles (DIN 53902,
Part 2)
2 1 99067 23
~able I
Verbindung a b+c+d+e x*R1Y*(R2+ R3 + R4)= R
gemaB Bei- Z*(R2+ R3 + R4)= R
spiel m*(R2+ R3 + R4)= H
3.1 3-6 10 1 y 0.5
z 1
m 2.5
3.2 3-6 10 1 y 0.5
z 1.75
m 1.75
3.3 3 0 1 y O
z 1.25
m 2.75
3.4 3 O .. 1 y O
z 1.5
m 2.5
3.5 3-6 0 1 y 0.5
z 1.5
m 2
3.6 3 0 1 y O
z 1.75
m 2.25
Key: l Compound according to Example
2199067 24
Table II
Beispiel aus Scha~.~vel~ ~en Calciumha ~e- RBC-Test Oberflachenspannung (Lecomte
Tabelle 1 mm (Ross-M.) ver- L/D-Wert de Nouy) mN / mm
- sofort / S min traglichkeit 0.1 % 0.01
3.1 135 / 125 V > 100 35.7 38.9
3.2 140 ~ 130 V > 100 33.2 35.6
3.3 130 / 125 V > 100 36.8 38.7
3.4 140 / 130 V > 100 34.8 37.5
3.5 130 / 115 V > 100 38 4 39.1
3.6 140 / 125 V > 100 36.6 38.6
Key: 1 From Table I
2 Foaming capacity mm (Ross-M.), immediately/5 min
3 Calcium hardness tolerability
4 RBC test, L/D value
S Surface tension (Lecomte de Nouy) mN/mm
2 1 99067
Table III. Test formula skin cream
OE Rezeptur 1 2 3 4 5
splel 3.~ 2
~le~Jplel 3.5 - - - 2
Belsplel 3 . 6 2
Ste~rylalkohol- 2
~ethoxyl~t (3EO~
G~ REWOMUL0 MG 6 6 6 6 6
REWOPOL~ -- 2
SP FA 3~)
Cetyl~lkohol 2 2 2 2 2
p - -1~1 8 8 ô 8 8
Glycerln 3 3 3' 3
~cn~ervleronC n.B. n.B. n.~. n.B. n.~.
~e~ln. W~ser ad lOO ad 100 ad lOO ad 100 ad 100
bel ~ stabll~ lnstabll ~ tabll ~ stabll ~ tabll
O ~C
.. us~ehen ~latte, wel~e qrlesig, Emul- o Jltte, uelBe glatte, weiBe glatte welBe
Creme ~ ~ lon brlcht1~ ~ eme ~Creme ~ Créme
[ad = up to]
Key: 1 Formula
2 Example 3.4
3 Example 3.5
4 Example 3.6
Stearyl alcohol ethoxylate (3EO)
6 REWOMUL~ MG
7 REWOPOL~ SB FA 30
8 Cetyl alcohol
9 Paraffin oil 3.5~E
Glycerin
11 Preservation
12 Demineralized water
13 Stability of the emulsion at 5~, 20~ and 40~C
14 Stable
Unstable
16 Appearance
17 Smooth, white cream
18 Gritty, emulsion break
The properties on the skin were described, by a selected
test panel, as easily spread and easily penetrating for formulas
3, 4, and 5. A smooth, pleasant feeling on the skin was also
confirmed.
21 9qO67
26
Table IV. Mild baby shampoo
Rezeptur 1 2 3
Belspiel 3.5 - 25
Beispiel 3.6 - - 25
O~-~IC0 AM B 45 11 11 11
REWOPOL~ SB FA 30 25
k~wO~K~ LI S 80 5 5 5
NaCl 2 2 2
Wasser ad 100 ad 100 ad 100
RBC-WERT (L/D) 4 > 100 > 100
tad = up to3
Key: 1 Formula ' ~
2 Example 3.5
3 Example 3.6
4 REWOTERIC~ AM B 45
REWOPOL~ SB FA 30
6 REWODERM~ LI S 80
7 NaCl
8 Water
9 RBC-VALUE (L/D)
Using the compounds according to the invention, the
dermatological tolerability of the formulas could be decisively
improved.
21 99067
27
Table V. Skin-friendly dishwashing agent for manual use
Rezeptur 1 2 3
Beispiel 3.1 - 3
Beispiel 3.2 - - 3
REWOPOL0 NL 2-28 18 18 18
REWOTERIC~ AM CAS 1.5
REWOPAL0 LA 6 1.5
demin. Wasser ad 100 ad 100 ad 100
Viskositat, mPas, mlt
NaCl eingestellt
RBC-Wert, L/D 0.8 ' 1.4 1.5
Schaumvermogen, mm190 / 185 780 / 170 185 / 180
+ 1 ml Olivenol
190 / 185 180 / 170 185 / 180
[ad = up to]
Key: 1 Formula
2 Example 3.1
3 Example 3.2
4 REWOPOL~ NL 2-28
REWOTERIC~ AM CAS
6 REWOPAL~ LA 6
7 Demineralized water
8 Viscosity, mPas, adjusted with NaCl
9 RBC-value, L/D
Foaming capacity, mm ~ 1 mL olive oil
The use of the compounds according to the invention leads to
an improvement of the skin tolerability of the formulas without a
negative influence on the surfactant properties of the
formulation.
- 2 1 99067
28
Table VI. Mild shower gel
Rezeptur 1 2 3 4
Beisplel 3.2 - 12
B~ispiel 3.4 - - 12
Belspiel 3.5 - - - 12
R~w~u ~ SB FA 30 12
R~wu,~IC~ AM G 30 20 20 20 20
REWODERM0 LI 48-50 7.5 7.5 7.5 7,5
Citron~ncA-lreca. 0.1 ca. 0.1 ca. 0.1 ca. 0.1
Wasser, Ronserv. ad-100 ad 100 ad 100 ad 100
~autgefuhl~ etwas rauh glatt ~ ngenehm, glatt ~ ng~n~h~ ~hr angenehm,
SchA ~truktur~ robblasig~ cremig~ einblasig,~ cremig
[ca. = approximately]
[ad = up to]
Key: 1 Formula
2 Example 3.2
3 Example 3.4
4 Example 3.5
REWOPOL~ SB FA 30
6 REWOTERIC~ AM G 30
7 REWODERM~ LI 48-50
8 Citric acid
9 Water, preservation
Feeling on skin
11 Slightly rough
12 Smooth, pleasant
13 Very pleasant, smooth
14 Foam structure
Large bubbles
16 Small bubbles, creamy
The examples according to the invention were evaluated in
the test formula by a test panel to determine their foaming
capacity, [immediate] feeling on the skin, and feel on the skin
after drying of the skin.
- 2199061
Table VII. Hair rinse
Rezeptur 1 2 3
Beispiel 3.2 2 - -
Beispiel 3.4 - 2
Beispiel 3.5 - - 2
REWOPOL0 SB FA 30 ca. 1 ca. 1 ca. 1
REWOQUAT~ WE 38 3.3 3.3 3.3
DPG
Wasser, Ronserv. ad 100 ad 100 ad 100
Trockenkammbarkeit ~ ~sehr gut ~ sehr gut ~ sehr gut
~ b-' ' ? rkeit ~ sehr gut ~ gut ~ 5 sehr gut
[ca. - approximately]
tad = up to]
Key: 1 Formula
2 Example 3.2
3 Example 3.4
4 Example 3.5
REWOPOL~ SB FA 30 ~ ~
6 REWOQUAT~ WE 38
DPG
7 Water, preservation
8 Dry combing ability
9 Very good
Wet combing ability
11 Good
The examples according to the invention were evaluated in
the test formula by a test panel to determine the dry and wet
combing ability.
21 9~067
Table VIII. Hair shampoo 2 in 1, ultramild
Re~eptur 1 2 3
Beispiel 3.2 5 - -
Beispiel 3.4 - 5
Beispiel 3.5 ~ ~ 5
~REWOPOL~ NL 2-28 30 30 30
~w~l~KIC~ AM ~ 50 7 7 7
REWOQUAT~ CPEM 1.5 1.5 1.5
R~WO~K~0 LI S 80 ca. 2 ca. 2 ca. 2
Wasser, Konserv. ad 100 ad 100 sd 100
NaB~:- '?rkeit ~ $sehr gut~ sehr gut ~ sehr gut
HaarfulleCsehr gut U~ gut ~ gut
~ca. - approximately]
[ad = up to]
Key: 1 Formula
2 Example 3.2
3 Example 3.4
4 Example 3.5
REWOPOL~ NL 2-28 ' ~
6 REWOTERIC~ AM B 50
7 REWOQUAT~ CPEM
8 REWODERM~ LI S 80
9 Water, preservation
Wet combability
11 Very good
12 Hair fullness
13 Good
The examples according to the invention were evaluated in
the test formula by a test panel to determine hair fullness and
wet combing ability.
