CA2199067A1 - Polyglycerin ester sulfosuccinates, method for their preparation, and their use - Google Patents
Polyglycerin ester sulfosuccinates, method for their preparation, and their useInfo
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- CA2199067A1 CA2199067A1 CA 2199067 CA2199067A CA2199067A1 CA 2199067 A1 CA2199067 A1 CA 2199067A1 CA 2199067 CA2199067 CA 2199067 CA 2199067 A CA2199067 A CA 2199067A CA 2199067 A1 CA2199067 A1 CA 2199067A1
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-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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- Birds (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to fatty acid ester sulfosuccinates 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 and/or inorganic bases.
Description
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 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.
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 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.
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 0.5-25 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.
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 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 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 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 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 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 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 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 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 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 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 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) ~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 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 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 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.
Table V. Skin-friendly dishwashing agent for manual use Rezeptur 1 2 3 Beispiel 3.1 - 3 Beispiel 3.2 - - 3 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 [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.
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.
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.
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 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.
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 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.
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 0.5-25 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.
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 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 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 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 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 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 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 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 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 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 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 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) ~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 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 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 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.
Table V. Skin-friendly dishwashing agent for manual use Rezeptur 1 2 3 Beispiel 3.1 - 3 Beispiel 3.2 - - 3 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 [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.
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.
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.
Claims (8)
1. Fatty acid ester sulfosuccinates of general formula 1 (1) with the meanings R1 = FR [sic; FS]-CO, where FS is a C7-21 hydrocarbon residue that optionally contains multiple bonds and/or is optionally substituted with one or more OH groups R2 = R1 or -CO-CH(SO3-X+)-CH2-COO-X+ or -CO-CH2-CH(SO3-X+)-COO-X+
R3, R4 = the same or different = H, R1, R2, EO = the residue -CH2-CH2-O- with a, b, c, d, e = 0-5 X+ = H+ or a cation, which is 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 and/or mineral bases.
R3, R4 = the same or different = H, R1, R2, EO = the residue -CH2-CH2-O- with a, b, c, d, e = 0-5 X+ = H+ or a cation, which is 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 and/or mineral bases.
2. Compounds of general formula (1) according to Claim 1, characterized in that R1 = FS-CO with FS = fatty acid and R2, R3, and R4 = at least once [are equal to]
and otherwise = H, and a = 1-4 and b, c, d, e = 0.
and otherwise = H, and a = 1-4 and b, c, d, e = 0.
3. Method for the preparation of compounds of general formula (1) (1) with the meanings R1 = FR [sic; FS]-CO, where FS is a C7-21 hydrocarbon residue that optionally contains multiple bonds and/or is optionally substituted with one or more OH groups R~ = R1 or -CO-CH(SO3-X+)-CH2-COO-X+ or -CO-CH2-CH(SO3-X+)-COO-X+
R3, R4 = the same or different = H, R1, R~, EO = the residue -CH2-CH2-O- with a, b, c, d, e = 0-5 X+ = H+ or a cation, which is 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 and/or mineral bases.
R3, R4 = the same or different = H, R1, R~, EO = the residue -CH2-CH2-O- with a, b, c, d, e = 0-5 X+ = H+ or a cation, which is 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 and/or mineral bases.
4. Hair rinse, containing a) 1-40 parts by weight of the compound of general formula (1) b) 1-40 parts by weight of at least one nonionic, amphoteric, zwitterionic, cationic, or anionic surfactant, and c) 0.1-10 parts by weight of a thickener, scent, preservation agent, dye, plant extract, or other additive and auxiliary substance, and optionally d) water up to 100.
5. Aqueous hair shampoo, containing a) 1-40 parts by weight of the compound of general formula (1) b) 1-40 parts by weight of at least one nonionic, amphoteric, zwitterionic, or ionic surfactant, and c) 0.1-10 parts by weight of a thickener, scent, preservation agent, dye, plant extract, or other additive and an auxiliary substance, and optionally d) water up to 100.
6. Aqueous dishwashing agent, containing a) 1-15 parts by weight of at least one of the compounds of general formula (1), and b) 1-40 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, and ionic surfactants and, optionally c) 0.1-10 parts by weight of a thickener, scent, preservation agent, dye, plant extract, and other additives and auxiliary substances and, optionally, d) water up to 100.
7. Skin care agent, containing a) 1-10 parts by weight of at least one of the compounds of general formula (1), and b) 1-10 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, and ionic surfactants and, optionally c) 2-10 parts by weight of plant oils, or mineral oils, or ester oils, d) 1-5 parts by weight of a consistency imparting agent e) 0.5-5.0 parts by weight of a scent, dye, or preservation agent f) water up to 100.
8. Skin cleaning agent, containing a) 1-10 parts by weight of at least one of the compounds of general formula (1) and b) 0.1-20 parts by weight of at least one surfactant from the group of nonionic, amphoteric, zwitterionic, and ionic surfactants and, optionally c) 0.1-10 parts by weight of a thickener, scent, preservation agent, dye, plant extract, and other additives and auxiliary substances and, optionally d) water up to 100.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996108367 DE19608367A1 (en) | 1996-03-05 | 1996-03-05 | Polyglycerol ester sulfosuccinates, process for their preparation and their use |
| DE19608367.2 | 1996-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2199067A1 true CA2199067A1 (en) | 1997-09-05 |
Family
ID=7787210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2199067 Abandoned CA2199067A1 (en) | 1996-03-05 | 1997-03-04 | Polyglycerin ester sulfosuccinates, method for their preparation, and their use |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0794173A3 (en) |
| CA (1) | CA2199067A1 (en) |
| DE (1) | DE19608367A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130204021A1 (en) * | 2012-02-03 | 2013-08-08 | Evonik Industries Ag | Polyglycol ether-free sulphosuccinates based on polyglycerol partial esters and use thereof |
| CN104066715A (en) * | 2012-02-03 | 2014-09-24 | 赢创工业集团股份有限公司 | Polyglycol-ether-free sulfosuccinates based on polyglycerin partial esters and use thereof |
| CN106750261A (en) * | 2017-01-12 | 2017-05-31 | 温州大学 | A kind of preparation method of the polymer fatliquoring agent with sulfosuccinate ester salt structure |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010002609A1 (en) | 2010-03-05 | 2011-09-08 | Evonik Goldschmidt Gmbh | Partial ester of a polyglycerol with at least one carboxylic acid and a polyfunctional carboxylic acid, their preparation and use |
| CN106866472A (en) * | 2017-01-04 | 2017-06-20 | 温州大学 | A kind of polymer fatliquoring agent containing sulphite structure and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1054244A (en) * | 1900-01-01 | |||
| US2605293A (en) | 1951-04-26 | 1952-07-29 | Shell Dev | Production of glycerine |
| US2810768A (en) | 1954-04-19 | 1957-10-22 | Shell Dev | Production of glycerine |
| DE2700072A1 (en) | 1977-01-03 | 1978-07-13 | Henkel Kgaa | EMULSIONS FOR EMULSION POLYMERIZATION |
| SU679577A1 (en) * | 1977-03-15 | 1979-08-15 | Тульский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Химической Промышленности | Derivatives of polyglycerin and sulpho-amber acid as surfactants |
| DE3410520A1 (en) | 1984-03-22 | 1985-09-26 | Deutsche Solvay-Werke Gmbh, 5650 Solingen | Process for the preparation of polyglycerols by purification and separation of an aqueous solution of a polyglycerol-containing product |
| DE3600388A1 (en) | 1986-01-09 | 1987-07-16 | Solvay Werke Gmbh | METHOD FOR SEPARATING AND CLEANING POLYGLYCERINES OR RESIDUES CONTAINING POLYGLYCERINE |
| GB8804143D0 (en) | 1988-02-23 | 1988-03-23 | British Petroleum Co Plc | Fabric conditioners |
| DE4111807A1 (en) * | 1991-04-11 | 1992-10-15 | Rewo Chemische Werke Gmbh | FATTY ACID MONOGLYCERID POLYGLYCOLETHERSULFOSUCCI NATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE4136579A1 (en) * | 1991-11-07 | 1993-05-13 | Rewo Chemische Werke Gmbh | POLYOLPOLYETHERSULFOSUCCINATE, PROCESS FOR THEIR PREPARATION AND THEIR USE |
| DE4141532A1 (en) * | 1991-12-17 | 1993-06-24 | Henkel Kgaa | METHOD FOR PRODUCING HYDROPHILIZED TRIGLYCERIDES |
| JPH073287A (en) * | 1993-06-18 | 1995-01-06 | Lion Corp | Detergent composition |
-
1996
- 1996-03-05 DE DE1996108367 patent/DE19608367A1/en not_active Withdrawn
-
1997
- 1997-02-14 EP EP97200426A patent/EP0794173A3/en not_active Withdrawn
- 1997-03-04 CA CA 2199067 patent/CA2199067A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130204021A1 (en) * | 2012-02-03 | 2013-08-08 | Evonik Industries Ag | Polyglycol ether-free sulphosuccinates based on polyglycerol partial esters and use thereof |
| CN104066715A (en) * | 2012-02-03 | 2014-09-24 | 赢创工业集团股份有限公司 | Polyglycol-ether-free sulfosuccinates based on polyglycerin partial esters and use thereof |
| US8993792B2 (en) * | 2012-02-03 | 2015-03-31 | Evonik Industries Ag | Polyglycol ether-free sulphosuccinates based on polyglycerol partial esters and use thereof |
| CN104066715B (en) * | 2012-02-03 | 2017-04-26 | 赢创德固赛有限公司 | Polyglycol-ether-free sulfosuccinates based on polyglycerin partial esters and use thereof |
| CN106750261A (en) * | 2017-01-12 | 2017-05-31 | 温州大学 | A kind of preparation method of the polymer fatliquoring agent with sulfosuccinate ester salt structure |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0794173A2 (en) | 1997-09-10 |
| DE19608367A1 (en) | 1997-09-11 |
| EP0794173A3 (en) | 1997-12-29 |
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