DE19620792A1 - Binary mixtures for making semi synthetic toilet soaps - Google Patents

Abstract

Preparation of components for semi-synthetic toilet soaps comprises preparing binary mixtures of at least partially saponified fatty acids with synthetic surfactants. Preferably the fatty acid or soap is added in excess, optionally during the preparation of the surfactant. The tallow to coconut or palm seed ratio in the soap/fatty acid component is 90-40:10-60. The unsaponified fatty acid content is 0-50 (5-15)%.

Description

The invention relates to the production of binary mixtures partially or completely saponified fatty acids with one each anionic, nonionic or amphoteric surfactant and their Use in semi-synthetic fine soaps.

Soap in the form of alkaline salts from naturally derived fatty acids is the oldest known body cleanser. During the technical development, it was continuously improved until today's quality standard of modern high quality toilet soaps. In addition to their positive processing and usage properties however, soap has some negative characteristics, e.g. B. Incompatible with hard water and sensitive skin.

With the large-scale availability of synthetic interfaces active substances, hereinafter called surfactants, was therefore tried to overcome these disadvantages of a toilet soap by complete or to eliminate partial substitution of fatty acid soap. The As a result of these efforts, so-called syndet soaps (syndets, Syndetbars) or semi-synthetic soaps (combo bars, combars). The status of the corresponding technologies is in the literature described, e.g. B. M. Hollstein and L. Spitz, JAOCS 59 (1982) 442; Z. Piso and C. A. Winder, Soap, Syndet and Soap / Syndet Bar Formulations,  in: L. Spitz (Editor), Soap Technology for the 1990′s, American Oil Chemists ′ Society, Champaign 1990, p. 209 ff. . Semi-synthetic Soaps are said to have the benefits of fatty acid soap with those of syndets unite in themselves without showing their disadvantages, above all inexpensive raw materials and manufacturing, good foam and Ver swamping behavior and especially good skin and mucous membranes compatibility.

A variety of surfactants have been used in combination with fatty acid soap proposed, mostly as multi-component mixtures. So describes WO 92/16609 as mixture components Na cocoyl glyceryl ether sulfonate and sodium lauroyl sarcosinate in combination with fatty acids and their magnesium salts. She describes transparent combo bars USP 4,963,284, wherein Na cocoyl isethionate together with Na Lauryl ether carboxylates and / or Na lauryl sulfate or cocoyl taurate as Mixture of surfactants is combined with soap. Use too other commercially available surfactants such as sulfosuccinates and cocoamidopropyl betaine in combination with fatty acids or their soaps is known (EP 0542526 A1).

The semi-synthetic toilet soaps are manufactured in usual procedure by mixing the individual components in a kneading mixer, homogenizing the mass in a roller mill and / or extruder and subsequent extrusion in one strand press with cutting and punching or direct molding to soap bars. These methods are prior art as such described in the specialist and patent literature and not subject matter the invention.

The combo bars produced in this way can contain soap or fatty acids and surfactants fillers, plasticizers and in addition to color and smell substances other additives to improve the properties of use contain. The water content is mostly depending on the formulation between 3 and 15%. Higher water contents lead to processing problems in the manufacture and deterioration of some Usage properties such as swamping and abrasion.  

The reduction in water content can be achieved in two ways, either by drying an aqueous solution or dispersion the mixture before the actual processing or by mixing of components with a correspondingly low water content. The former requires a high technical effort for drying facilities like spray dryers or surface evaporators, about which many Manufacturers of toilet soaps do not have them. On the other hand, it is Possible use of largely water-free synthetic surfactants limited, since these are often in z. B. powder or granular form are not or can only be manufactured and delivered at high costs. This often results in a severe narrowing of the wording freedom and recipe optimization.

Further problems arise with powdered surfactants, their Dust formation during processing additional work and environmental protection requires, e.g. B. suction and separation devices.

It was therefore the task of making surfactants easy to process To provide components for combo bars, the above Do not have disadvantages. According to the invention, the Combination of a surfactant with soap or fatty acid in Form of a binary compound found. In this sense it is Matrix soap / fatty acid as the one component of the compound Are defined.

Binary mixtures of soap or fatty acids with surfactants are in themselves known. For example, the soaps on the market chemically related Na fatty acid isethionate shares of approx. 10% Fatty acid or soap as manufacturing-related impurities (Examples: Arlatone SCI from ICI Surfactants, Elfan AT 84 from Akzo Chemicals). These parts can be deliberately higher during production can be set to achieve special physical properties.  

For example, DE 42 36 502 A1 describes the production of soaps Fatty acid isethionates with the addition of 10-25% fatty acids and their Soap. The mixtures contained remain homogeneous and under 100 ° C flowable. Your use u. a. for the production of "syndet soap" is mentioned, but remains on the surfactant class of the isethionates limited. So there is no technical solution, combo bars with one greater selection of surfactants, each in combination with Soap / fatty acid present, largely variable and complex in one to be able to formulate and produce in a simple manner.

DE 37 03 258 A1 describes the combination of soap with at least a surfactant with additives as skin-friendly Soap-based personal care products. A possible use as Component for the production of semi-synthetic soaps will not mentioned. The range is the soap: surfactant mixture ratio 92: 3 to 65:30, preferably 85: 10 to 75: 20. As a surfactant The only components are carboxymethyl ether oxyethylated fat called acid derivatives and fatty alcohols, which are already in relative small amounts are effective on the skin. Here is the Combination not limited to piece-shaped body care products, but extended to liquid or pasty dosage forms. Mixtures of soap with surfactants other than those claimed Carboxymethyl ethers are considered not due to their consistency satisfactorily processable.

It has now been found that easily processable components for half synthetic toilet soaps can be obtained by a process can, which is characterized in that the components in the form binary mixtures of completely or only partially saponified Fatty acids with anionic, nonionic or amphoteric synthetic Surfactants are made.

The wholly or partly in the form of soap Fatty acids are defined as the one component of the component  which as a matrix for each synthetic surfactant as the other Part of the component serves to make it processable Improve and simplify combo bars. The proportion of unsaponified, free fatty acids to soaps / fatty acid content can be between 0 and 50% lie; preferably it is 5-15%. The admixture of fat Acids can advantageously already "in situ" during production of the surfactant or afterwards. In the first case, the any fatty acid used for the reaction in the corresponding Excess used and in the end partially or completely neutralized. Excess water is removed through common drying processes such as for example spraying, surface evaporation, freeze drying, etc. away. The binary mixtures are left on a residual water content from 0-20%, preferably 3-15% dried. Depending on the drying and type of discharge, granules, flakes, pallets or the like are obtained suitable forms of delivery.

The mixing ratio of soap / fatty acid to synthetic surfactant is in the range from 10:90 to 90:10, in each case based on active substance, preferably in the range 25:75 and 40:60. This is sufficient Guaranteed scope for the final formulation of the combo bars. However, conditions outside of this range are also possible. Surprisingly, it was found that even with relatively low Proportions such as B. 10-30% of wholly or partially saponified Fatty acids largely solid, waxy binary tenside compounds are available in easily processable form. In contrast to result in many commercially available surfactants on their own among analog Drying conditions tough, sticky masses that are so difficult to process are. For this reason, they are mostly only in aqueous solutions in trade, e.g. B. Na lauryl ether sulfate, cocoamidopropyl betaine or Alkyl polyglycosides.

The soap / fatty acid component of the components according to the invention the cuts commonly used in the soap industry  Coconut, palm oil, palm kernel and tallow fatty acids in question, so in particular the common "basic soap" mixtures tallow: coconut or palm kernel from 90: 10 to 40: 60. Free fatty acids bring about the properties of "over-greased" soap and serve equally as a matrix component. They also improve the workability and structure of the resulting pieces. The proportion of unsaponified, free fatty acids in the soap / fatty acid content can range between 0 and 50% lie; preferably it is 5-15%.

Coming as the respective synthetic surfactant component of the components all synthetic materials suitable for cosmetic applications surfactants in question. From the group of anionic surfactants are, for example, sulfates, carboxylates, Sulfosuccinates, sulfoacetates, phosphates of alkyl and alkyl ethers residues, sulforizinoleates, sulfofatty acid esters, taurides, sarcosinates and alkyl glyceryl ether sulfonates. Suitable nonionic surfactants are fatty acid, fatty alcohol and triglyceride ethoxylates, fatty acid alkanolamides and alkyl polyglycosides. Coming as amphoteric surfactants in particular fatty acid amidoalkyl betaines and amphodiacetates in question. The binary components produced according to the invention are described in usual soap systems to piece-shaped semi-synthetic Toilet soap processed. For this, they are alone according to the recipe or combined with basic fatty acid soap and additives mixed, homogenized, extruded and pressed into pieces. Special facilities are not required. Additions Auxiliary substances such as paraffins, fatty alcohols, glycerides etc. are possible.

The following examples are intended to explain the invention in greater detail, without to limit them to that.

A) Production of the components

Due to the batch sizes on a laboratory scale was used as drying freeze drying method selected. Other drying processes are equally suitable.

example 1 Na cocoylamidopropyl betaine

258 g dimethylaminopropylamine were mixed with coconut oil fatty acid in 60% molar excess to the corresponding amidamine in a known process implemented wisely. The subsequent quarternation also took place in usual reaction by equimolecular implementation of Amidamins with Na monochloroacetate in aqueous NaOH-alkaline medium. The result was a yellowish, slightly opaque, highly viscous product, after drying as a beige, waxy component the following composition existed:

65% cocoamidopropyl betaine
22% coconut oil fatty acid, Na salt
9% table salt (reaction by-product)
4% water

Example 2 Na lauryl ether sulfosuccinate

0.69 mol lauryl alcohol polyglycol ether (3 EO) were known in Way with 0.74 mol maleic anhydride to the corresponding half ester implemented and then with 0.75 mol Na sulfite in the presence of a equimolar mass of Na hydroxide to sulfosuccinic acid half-ester sulfites. Then 0.16 mol of coconut oil fatty acid at 50 ° C. stirred in and with about 4 g of 45% aqueous NaOH solution on a Neutralized pH 7-8. The viscous, yellow and almost colorless Mixture gave an almost white waxy component after drying approximately the following composition:

86% sulfosuccinate
10% coconut oil fatty acid, Na salt
4% water

Examples 3-6 Other anionic surfactants

The binary components listed here were made by mixing a tallow / coconut base soap mass, each with a commercially available anionic surfactant and then drying. Depending on The residual water content was the soap / fatty acid content 23-25%. Na salts were present in all cases.

Example 7 Coconut fatty acid diethanolamide

By mixing at about 130 ° C a compound with 90% non-ionic Ingredient and 10% soap made. Alternatively, one correspondingly over-stoichiometric addition of fatty acid in the Synthesis of diethanolamide with subsequent partial, if necessary Saponification take place. It resulted in a light colored soft, wax like mass.

Example 8 Ethoxylated isostearic acid monoglyceride

A binary component of 80% was obtained by mixing at approx. 130 ° C non-ionic surfactant and 20% soap. The compound was yellowish and soft-pasty.  

Example 9 Alkyl polyglucoside

As in Examples 3-6, a 75% nonionic compound became Surfactant (Glucopon 600 CSUP, Henkel KGaA) and 25% soap, based on the solid obtained after drying. It resulted an almost white, soft wax.

B) Processing the components into semi-synthetic toilet soaps

The components of the invention are used alone or in under different combinations together with soap and possibly fatty acids mixed in a Z-kneader, piled on a roller mill (homogenized) and extruded through a duplex vacuum extruder. After being cut onto blanks, press them with a soap punch Pieces were subjected to comparative, typical used tests. The following recipes are intended to illustrate the diverse possibilities explain the processing to combo bars as an example. The However, use according to the invention is not restricted to this.

To better compare processing and usage properties can, was based on additives of active substances and dyes as well as perfume no oil. Such additives correspond to the prior art and are easy to incorporate here.

Example 10 Combar with Na lauryl ether sulfate

33.3 parts by weight of the compound from Example 4 were 56.7 Parts of tallow-coconut base soap and 10 parts of stearic acid mixed, piliert and extruded at 48 ° C head temperature in an extrusion press. The pieces pressed from the blanks were homogeneous, sufficient hard and opalescent. Their composition corresponded

26.1% Na lauryl ether sulfate
60.1% Na soap
10.1% fatty acid
3.4% water

The pH of a 10% aqueous solution was 8.7. in the Use test showed the pieces to foam well and one fine-bubble stable foam with a cream-like structure.

Example 11 Combar with Na Laurylsulfoacetate

33.3 parts by weight of the compound from Example 4 were 33.3 Parts of the compound from Example 5 and 33.4 parts of basic soap mixed, piled and extruded at 44 ° C. The resulting Pieces showed sufficient hardness and had a homogeneous, shiny white appearance. They corresponded to the following composition:

25.0% Na lauryl ether sulfate
24.2% Na lauryl sulfoacetate
45.1% Na soap
5.7% water

The pH of a 10% aqueous solution was 9.6. The utility properties were judged equally positively as in Example 10.

Example 12 Combar with Na Lauryl ether sulfosuccinate and Na Lauryl sulfoacetate

29.4 parts by weight of the compound from Example 2 were 33.3 Parts of the compound from Example 5 and 27.3 parts of basic soap and 10 parts of stearic acid processed as in Examples 10 and 11 (Head temperature 45 ° C). The resulting pieces were hard homogeneous and smooth white. They had the following composition:

25.2% Na lauryl ether sulfosuccinate
24.0% Na lauryl sulfoacetate
35.1% Na soap
10.0% stearic acid
5.7% water

The pH of a 10% solution was 9.1. The utility ones properties corresponded to those in Examples 10 and 11.

Claims (9)

1. A process for the production of components for semi-synthetic toilet soaps, characterized in that the components are produced in the form of binary mixtures of completely or only partially saponified fatty acids with synthetic surfactants. 2. The method according to claim 1, characterized in that the Fatty acid or soap contents, if necessary, during production of the synthetic surfactant to be added as a reactant be added in excess. 3. The method according to claims 1 and 2, characterized in that the soap / fatty acid content is usually for toilets Soap used in sebum: coconut or sebum: palm kernel cuts in Correspond ratio of 90: 10 to 40: 60. 4. The method according to claims 1 to 3, characterized in that the percentage of unsaponified fatty acids is 0-50% in total, preferably 5-15%. 5. The method according to claim 1, characterized in that the synthetic surfactant components anionic, nonionic or are amphoteric. 6. The method according to claim 5, characterized in that the respective synthetic surfactant a sulfate, carboxylate, sulfosuccinate, sulfoacetate, Phosphate of an alkyl or / and alkyl ether radical, sulforizinoleate, Sulfofatty acid esters, alkylglyceryl ether sulfonate, fatty acid sarcosinate or taurate, a fatty acid, fatty alcohol, Glyceride / polyol ethoxylate, fatty acid alkanolamide or alkyl polyglycoside, a fatty acid amidoalkyl betaine or amphodiacetate.   7. The method according to claims 1 to 6, characterized in that the mixing ratio of soap / fatty acid to synthetic Surfactant in the range from 10:90 to 90:10, in each case based on Active substance, is preferably between 25:75 and 40:60. 8. The method according to claims 1 to 7, characterized in that that the binary mixtures have a residual water content of 0-20%, preferably 3-15%, can be dried. 9. Use of binary mixtures of complete or only partially saponified fatty acids with synthetic surfactants components produced according to claims 1 to 8 alone or in combination with each other with or without the addition of Fatty acid soaps and / or free fatty acids for processing to semi-synthetic toilet soaps.