ES2302918T3 - SOAP PRODUCTS, CONFORMED, CONTAINING ONE OR MISCELLANEOUS DERIVED FROM ALMIDON PREGELATINIZED RETICULATED. - Google Patents

Abstract

Disclosed is a molded soap product containing a) one or several fatty acids comprising 12-22 C atoms in the form of the alkali soaps thereof, and b) one or several pregelatinized, cross-linked starch derivatives.

Description

Soap product, shaped, containing one or several pregelatinized crosslinked starch derivatives.

The present invention relates to agents cleaning cosmetics in the form of shaped soap products. This class of agents are already known. It is in essence of substances or mixtures of surfactant substances that are They offer the consumer in different forms of preparations.

Surfactants, the best known of which are the alkaline salts of fatty acids superior, namely the classic "soaps", are substances amphiphiles, that is, they can emulsify substances non-polar organic in water.

These substances drag not only the dirt of the skin and hair but stimulate, according to the surfactant or the chosen surfactant mixture, skin and mucous with greater or lesser strength. There is a large number of surfactants that are softer, although the surfactants that are available according to the current state of the art, they are soft and clean although bad, or clean well but do not stimulate the skin or mucous

Already in a simple water bath without adding surfactants first occurs a swelling of the layer cornea of the skin, where the degree of this swelling depends, by example, the duration of the bath and its temperature. The same time, wash or rinse, the soluble substances in water, p. e.g., water soluble dirt components, but also the skin's own substances that are the responsible for the capacity of union of the water with the cornea layer. Through the skin's own surfactant substances, they also dissolve skin fats to some extent, and they rinse This conditions after the initial swelling a obvious subsequent drying of the skin, which becomes more evident because of the additives that also exert an action Active in the wash.

Therefore it has been deemed convenient to put remedy to these inconveniences.

In healthy skin, these processes do not have in general importance, since the natural mechanisms of protection can compensate without further these slight inconveniences of the upper layers of the skin. However, in the case of non-pathological deviations from normal status, p. eg, because of environmental conditions, damage caused by wear, or respectively irritations, damage caused by light, skin aged, etc., the protection mechanism of the skin surface Depending on the circumstances, it is no longer in conditions of fulfilling its mission by itself and the skin must be regenerated by external measures. An objective of the present invention is therefore to remedy this lack of state of the art

In cleaning the body, the soaps in pieces they play a great role, and are currently obtained on a large scale by continuous saponification of free fatty acids with alkalis, concentration of the base soap formed, and dried by spray. In this respect, a distinction is made between true alkaline soaps, which are exclusively acid salts fatty and eventually still contain free fatty acids, and the called "Combibars" ("combi bars"), soap pieces which, together with the salts of fatty acids contain in addition other synthetic surfactants, as a rule, sulfates of ethers of fatty alcohols or fatty acid isothionates. A privileged position, however, occupies Syndet soaps ("synthetic detergents") in parts, the calls "Syndetbars" ("Syndet bars"), which do not form salts  of fatty acids, not even as impurities, and contain exclusively synthetic surfactants.

Only in Germany are sold annually several million pieces of soap for body hygiene. The Market requirements in this article of mass consumption are each higher Soap in pieces should not only clean the skin but also take care, that is, prevent the skin from becoming dry, grease it again and exert protection against influences of the outside. Naturally, the soap is expected to be compatible to some extent with the skin, and should form when used, the as much creamy foam as possible and communicate a sensation skin-friendly In this regard, soap manufacturers in pieces continually investigate the incorporation of new substances, which take into account this growing profile of requirements.

There is a difference between solid soaps, the most of the time in the form of pieces, and soaps liquids The main components are the alkaline salts of fatty acids from oils and natural fats, preferably with a chain length of 12 to 18 carbon atoms.

Since lauric acid soaps produce a lot of foam, coconut oils and palm kernels, rich in lauric acid, are the raw materials preferred for the manufacture of fine soaps. Sodium salts of the mixture of the respective fatty acids, are solid, and those of Potassium are soft, pasty. For saponification, the soda or diluted caustic potash, to fatty raw materials in stoichiometric ratio, such that in the finished soap, an excess of caustic bleach no greater than 0.05% is present. TO Often, today, soaps are obtained not directly from of fats, but from the fatty acids obtained from the Excision of fats.

Common additions to soaps are the fatty acids, fatty alcohols, lanolin, lecithin, oils vegetables, partial glycerides and other substances similar to greases for freshly cleansed skin, antioxidants such as ascorbyl palmitate or tocopherol to prevent autooxidation of soaps (thickening), forming agents of complexes such as nitrile triacetate to capture traces of heavy metals, which could catalyze self-oxidizing deterioration, perfume essences to achieve the desired fragrant notes, dyes to color the pieces of soap and if desired, additives special.

The most important types of fine soaps They are:

- soaps for personal hygiene with 20 - 50% coconut oil in the fat mixture, up to 5% of regreasing component and 0.5-2% perfume essence, they constitute the largest proportion of fine soaps;

- luxury soaps with up to 5% of one perfume essence particularly expensive;

- deodorant soaps with substances active deodorants like p. eg the 3,4,4'-trichlorocarbanilide (triclocarbano);

- creamy soaps with a proportion particularly high in regreaser and creamy substances for skin;

- baby soaps with a good regreasing and additional skin care components, such as p. eg chamomile extract, in any case very weakly scented;

- soaps for skin protection with a high proportion of re-greasing substances as well as others additives for skin care and protection, such as p. eg proteins;

- transparent soaps with additives from glycerin and sugar among others, which prevent crystallization  of fatty acid salts in soap melts when solidify, and thus provide an appearance transparent;

- floating soap with a density <1, characterized by controlled air bubbles during manufacturing;

- soaps with abrasive additives for cleaning of heavily soiled hands.

In washing with soap it is adjusted in the liquid wash a pH value of 8-10. This alkalinity neutralizes the Natural acidic layer of the skin (pH value 5 - 6). This value is recover in normal skin relatively quickly, in the case of a Sensitive or previously damaged skin may occur without However, irritations. Another disadvantage of soaps is the formation of lime soaps insoluble in hard water. These Disadvantages do not exist in Syndet soaps. The basis of them they are synthetic anionic surfactants, which together With fillers, re-greasers and other additives can be incorporated into pieces similar to soap. The pH value It is variable in wide limits and most of the time it is neutral, namely, with a pH 7, or conforms to the acidic layer of the skin regulating at pH 5.5. They have a magnificent cleaning power, they foam at any hardness of water, even in the water of sea, and the proportion of re-greasing additive must be clearly higher than in normal soaps because of its intensive action of Cleaning and degreasing. Its disadvantage is the price relatively tall.

Surfactants are amphiphilic substances, the which can dissolve in organic substances no polar. They provide, conditioned by the specific construction of its molecule, with at least one hydrophilic part and one part hydrophobic molecule, a decrease in surface tension of water, skin moisturization, facilitate removal and dissolution of dirt, they are easy to rinse, and - if you want - a foam regulation.

In the hydrophilic parts of the molecule of a surfactant, there are most of the time, groups polar functions, for example -COO <->, -OSO3 <2>, -SO 3 -, while hydrophobic parts represent by general rule of non-polar hydrocarbons. The Surfactants are generally classified by type and loading of the hydrophilic part of the molecule. In this regard, it They can differentiate four groups:

anionic surfactants,

? cationic surfactants,

amphoteric surfactants and

• nonionic surfactants.

Anionic surfactants have as groups functional as a rule, carboxylate, sulfate or sulphonate In aqueous solution they form in an acidic or neutral medium, negatively charged organic ions. Surfactants cationics are characterized almost exclusively by the presence of a quaternary ammonium group. In aqueous solution form in medium Acid or neutral positively charged organic ions. The amphoteric surfactants contain both anionic and cationic and therefore behave in aqueous solution according to the pH value, as anionic or cationic surfactants. In a strongly acidic medium have a positive charge and in a medium strongly alkaline a negative charge. On the contrary, in a pH neutral range are ionically amphoteric, as the following example:

RNH 2 + CH 2 CH 2 COOH X -

(at pH = 2) X - = any anion, e.g. ex. Cl -

RNH 2 + CH 2 CH 2 COO -

(at pH = 7)

RNHCH 2 CH 2 COO - B +

(at pH = 12) B + = any cation, p. ex. Na +.

They are typical, in the case of non-surfactants ionic, polyether chains. Nonionic surfactants do not they form ions in an aqueous medium.

It is already known that fine soaps based on tallow and coconut fatty acids can be modified and be improved by numerous additives in its technical properties of utilization. In current books, p. eg Geoffrey Martin: The Modern Soap and Detergent Industry ("The Industry of modern soaps and detergents "), vol. 1, (1959), chapter VI, se describe inorganic fillers as alarming of the soaps, although p. eg, talcum powder, has rather an effect Disadvantageous in the soap in pieces. The addition of 5 - 20% talc Combi bars are described in DE 196 49 896. Through this addition, the smoothness and dispersing power of the lime soaps, improvement. U.S. Patent A-4 100 097 discloses a cleaning agent in pieces, which contains starch pregelatinized

The object of the invention consists in so much in providing a soap in pieces, that does not have the mentioned disadvantages. In this regard, we must have particularly note that the new soap compositions in parts must also be manufactured on an industrial scale, that is, that the compositions must, for example, have a formability high enough and when they dry they should not have a tendency to form cracks

It was surprisingly found that in the soap in Pieces containing one or more starch derivatives as an additive crosslinked, pregelatinized, chosen from the group of esters of hydroxypropylated phosphate, an improvement of the properties is achieved physical and technical application, in particular, the ability to washing and dispersion of lime soaps, and the smoothness of soap.

The invention is therefore a product of shaped soap, which contains:

a) one or more fatty acids with 12 to 22 atoms of carbon, in the form of its alkaline soaps, and

b) one or more starch derivatives pregelatinized crosslinks, chosen from the group of esters of hydroxypropylated phosphate.

Despite the small total content of surfactant substances in the formulation, the yield in Cleaning and foaming remain unchanged. The feeling on the skin improves decisively with the use of these pieces of washing, even without the addition of substances for the care of the skin.

The foam also acquires a better creaminess and more volume, which was not expected either. Another advantage of this invention is that it improves the tolerability of the wash piece, given that the total content of surfactants has been reduced.

Shaped soap products, according to the invention, they also have after the mechanical forming process,  a particularly smooth surface. When used, it produces a stable, creamy foam. The precipitate of calcium soap formed in hard water it remains dispersed in water and does not lead to formation of dirty gray deposits, on the surface of Sanitary objects.

Shaped soap products contain advantageously according to the invention, up to 99% by weight of a soap base, for example a soap whose components are formed by sodium tallowato (tallow = tallow in English), sodium cocoate and Sodium salt of fatty acid from palm kernels.

It is advantageous according to the invention, that one or various derivative (s) of starch, crosslinked (s), pregelatinized (s), is (are) contained in a concentration of 0.1 to 20% by weight, preferably in a concentration of 0.3 to 15% by weight, with a very particular preference, in a concentration of 0.5 to 10% by weight, referred to the total weight of the preparation, in the preparations according to invention.

According to the invention, they are used as derivatives of crosslinked, pregelatinized starch, phosphate esters hydroxypropylates, in particular, the hydroxypropyl diphosphate of starch. Employment is particularly preferred in this regard. of a hydroxypropyl starch diphosphate, such as that sold with the name of Structure® XL as a signature product National Starch

Soap products shaped according to In addition, they advantageously contain water in an amount of   0.5 - 35% by weight. The water content is due on the one hand to obtaining procedure and on the other hand said content acts favorably on the use properties of soap.

As fatty acids for soap making basic linear fatty acids with 12 to 22 atoms of carbon, p. e.g., lauric, myristic, palmitic, stearic acid, arachidic and behenic, but also unsaturated fatty acids, p. e.g., palmitoleic, oleic, linoleic, linolenic acid, arachidonic and erect. The use of technical mixtures is preferred, as obtained from vegetable fats and oils and animals, p. e.g., coconut oil fatty acids and acids tallow fatty Particularly preferred are mixtures of cuts of coconut and tallow fatty acids, in particular a mixture of 50-80% by weight of tallow fatty acids of 16-18 atoms of carbon and 20 - 50% by weight of coconut fatty acids from 12 - 14 carbon atoms

Fatty acids are used in the form of their alkaline soaps, usually as sodium soaps. But nevertheless. Soaps can also be obtained from fats and oils directly by saponification (hydrolysis) with caustic soda and glycerin separation. Preferably, the milled soap products according to the invention contain an additional proportion of 5-30% by weight of free fatty acids with 12-22 carbon atoms. These can be identical to the fatty acids in the base soap and can be incorporated into the base soap along with the corresponding alkali deficit, during saponification. However, it is preferred to add by dosing the free fatty acids, although after saponification and after concentrating, but before
dried

Eventually it may also be advantageous to add additional surfactants, to the base soap.

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As amphoteric surfactants they are used with advantage:

1. Acyl- / dialkylethylenediamine, for example, Sodium Acynaphoacetate, Disodium Acrylonodipropionate, disodium alkylophodiacetate, acyanofohydroxypropylsulfonate of sodium, disodium acilanfodiacetate and sodium acilanfopropionate, N-alkylamino acids, for example aminopropyl alkyl glutamide, acid alkylaminopropionic, sodium alkylimido dipropionate and lauroanfocarboxyglycinate.

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As anionic surfactants they are used with advantage:

Acylamino acids (and their salts), such as:

1. Acylglutamates, for example the sodium acylglutamate, the di-TEA-palmitoylaspartate and the Caprylic Sodium / Capric Glutamate,

2. Acylpeptides, for example protein palmitoyl-hydrolyzed milk, soy protein cocoyl-hydrolyzed sodium, and collagen sodium / potassium cocoyl hydrolyzate,

3. Sarcosinates, for example miristol sarcosine, TEA-lauroyl sarcosinate, the sodium lauroylsarcosinate and sodium cocoylsarcosinate,

4. Taurates, for example, the lauroiltaurato of sodium and the sodium methylcocoyl restaurant.

5. Acylactylates, lauroillactylate, and caproillactilate

6. The alaninates.

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The carboxylic acids and their derivatives, how:

1. Carboxylic acids, for example acid lauric, aluminum stearate, magnesium alkanolate, and zinc undecylenate,

2. The esters of carboxylic acids, by example calcium stearoillactylate, the lauret-6-citrate and the PEG-4-lauramidocarboxylate sodium,

3. The carboxylic ether acids, for example the sodium laureth-13-carboxylate and the PEG-6-cocamide carboxylate sodium,

Esters and salts of phosphoric acid, such as For example, him DEA-oleth-10-phosphate, and dilaureth-4 phosphate.

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Sulfonic acids and their salts, such as

1. Acyl isethionates, p. eg sodium / ammonium cocoyl isethionate,

2. The alkylarylsulfonates,

3. Alkylsulfonates, for example the sodium cocosmonoglycerides sulfate, sodium olefin sulphonate 12 to 14 carbon atoms, sodium lauryl sulfoacetate and the PEG-3 magnesium cocamidosulfate,

4. Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laurethsulfosuccinate, disodium lauryl sulfosuccinate, and the undecylenanamide-MEA-sulphosuccinate disodium

as well as

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Esters of sulfuric acid, such as

1. Alkyl ether sulfates, for example, sodium laureth sulfate, ammonium, magnesium, MIPA, TIPA, sodium mireth sulfate, and pareth sulfate (from 12 to 13 carbon atoms) of sodium,

2. The alkyl sulfates, for example the sodium lauryl, ammonium and ASD.

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As non-ionic surfactants it is advantageous use:

1. Alcohols,

2. Alkanolamides, such as cocamides MEA / DEA / MIPA,

3. Amino acids, such as cocoamidopropylaminoxide

4. Esters, which are obtained by esterification of carboxylic acids with ethylene oxide, glycerin, sorbitan or other alcohols,

5. Ethers, for example, alcohols ethoxylated / propoxylated, ethoxylated / propoxylated esters, ethoxylated / propoxylated glycerinesters, cholesterol ethoxylated / propoxylated, ethoxylated / propoxylated triglyceridesters,  Propoxylated ethoxylated lanolin, polysiloxanes ethoxylated / propoxylated, POE-propoxylated ethers, and alkyl polyglycosides such as lauryl glycoside, decylglycoside, and cocoglycoside,

6. Sucrose esters and ethers,

7. Polyglycerinesters, diglycerinesters, monogli-cerinesters,

8. Methylglucose esters, esters of hydroxy acids

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As cationic surfactants, it is advantageous use:

1. Alkylamines,

2. Alkylimidazoles,

3. Ethoxylated amines,

4. Quaternary surfactants and

5. Estercuatos.

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Quaternary surfactants contain at least minus one atom of N, which is covalently linked with groups 4-alkyl- and / or aryl groups. This leads, regardless of the pH value, at a positive charge. Advantageous quaternary surfactants are alkyl betaine, the alkyl amidopropyl betaine and the alkyl amidopropylhydroxysulfaine. They can also cationic surfactants are chosen within the meaning of the present invention preferably among the group of ammonium compounds quaternary, in particular, the chlorides or bromides of benzyltrialkylammonium, such as chloride benzyl dimethyl stearylammonium, in addition to the salts of alkyltrialkylammonium, for example the chloride or bromide of cetyltrimethylammonium, chloride or bromide alkyldimethylhydroxyethylammonium, chloride or bromide dialkyldimethylammonium, alkylamide ethyltrimethylammonium ethersulfate, alkylpyridinium salts, for example lauryl chloride or cetylpyrimidinium, imidazoline derivatives and compounds of character cationic such as aminoxides, for example alkyldimethylaminoxides or alkylaminoethyldimethylamino oxides. In particular, the salts of Cetyltrimethylammonium are advantageous to use.

It is known according to the invention, the absence of alkyl- (oligo) -glycosides, alkyl- (oligo) -glycosides. The nonionic surfactants that can be purchased in trade, can be obtained through the relevant Organic Chemistry procedures and correspond to the formula R 1 -O (G) x, in which R 1 it is a primary alkyl group of 12 to 18 carbon atoms, and (G) x is an oligoglycoside radical, whose degree of oligomerization is x = 1 to 2. As representative of the copious existing literature, we refer here to patents EP-A-0 301 298 and WO-A-90/3977. The alkyl- (oligo) -glycosides can be derived from aldoses or ketoses with 5 or 6 carbons. Because of the ease with which they are obtained, they are manufactured on a large scale mainly the alkyl- (oligo) -glucosides derived from glucose. The absence of these substances means in any case, that they can be present in an elementary measure as impurities in a bar Combi according to the invention, although in any case, it must be less than 1% by weight.

Soap products shaped according to invention, may contain as other auxiliary substances and additives, oily bodies (grease for regreasing), emulsifiers, supergreasing agents, greases, waxes, stabilizers, polymers cationic, silicone compounds, pigments, active substances biogens, preservatives, dyes and substances odoriferous

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As greases to re-fat to use according to the The invention can be used advantageously for example:

1. Long chain alcohols, p. eg lanolin, cetyl alcohol,

2. Mono and diglycerides or respectively corresponding glycol esters,

3. Mono, di and triglycerides of plant origin p. e.g. almond oil,

4. Hydrogenated fats

5. Vaseline

6. Waxes.

As fat for regreasing also enter in consideration, for example oily bodies such as alcohols Guerbet based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear fatty acids from 8 to 20 carbon atoms with linear fatty alcohols of 6 to 20 atoms of carbon, branched carboxylic acid esters from 6 to 13 carbon atoms with linear fatty alcohols of 6 to 20 atoms of carbon, esters of linear fatty acids of 6 to 18 atoms of carbon with branched alcohols, in particular the 2-ethylhexanol, esters of linear fatty acids and / or branched with polyhydric alcohols (e.g., dimer diols or trimer diols) and / or triglycerides of Guerbet alcohols based on fatty acids of 6 to 10 carbon atoms, vegetable oils, branched primary alcohols, substituted cyclohexanes, Guerbetcarbon dialkyl ethers and / or aliphatic hydrocarbons or naphthenic respectively.

Finally, shaped soap products according to the invention, they may contain odoriferous substances and others usual auxiliary substances and additives in an amount of Up to 5% by weight. Appropriate auxiliary substances are p. eg binders or plasticizers. As such they are appropriate p. eg, the glycerin, partial glycerides of fatty acids or fatty alcohols with 12-22 carbon atoms.

Other auxiliary substances are p. eg dyes, antimicrobial substances, active substances deodorants, pigments (TiO2), optical brighteners and complex trainers.

Obtaining soap products formed according to the invention can be carried out in the manner usual for soaps. First of all it is obtained from the mixture of fatty acids and caustic soda, a base soap with a Fatty acid content of 25-50% by weight, and concentrated to a solids content of 50-70% by weight. In this base soap p. eg, 60%, can already be incorporated by mixing, talc, possibly also, free fatty acids, a surfactant amphoteric and a complexer. Then water is removed of the base soap, p. e.g., in a 120 ° C vacuum expansion dryer at 130 ° C. In the expansion process the soap cools spontaneously at temperatures below 60 ° C and solidifies. This results in soap strips with a solids content of 73-85% by weight.

The finishes of this base soap constitute the Manufacture of fine soap. This is achieved in a soap mixer in which they are incorporated, mixing, a grout of the amphoteric surfactants and other auxiliary substances and soap tape additives. In this way the soap tapes base and grout based on the surfactant (s) amphoteric (s) and p. eg odoriferous substances, dyes, pigments and other auxiliary agents mix intensely in a helical mixer with a sieve with holes, and finally it is transported to an extrusion press and eventually a press pieces, when the soap should be manufactured in pieces.

Soap products shaped in the sense of the invention may also be in the form of strips, needles, granulated, extruded, flakes and in any other way usual for soap products.

Alternatively to the procedures described, talc can be incorporated during manufacturing, only in one 73 - 85% of the base soap. In this case, the talcum powder is incorporates by suitable dosing devices, e.g. eg, some tape scales and a stirring doser together with the slurry of amphoteric surfactants, odoriferous substances and auxiliary substances in the soap mixer.

The soap products according to the invention are characterized by a particularly smooth surface, which in particular in the finishes of the soap in pieces does it especially nice. When used, it forms a creamy foam filled with fine bubbles In hard water form effectively precipitates of calcareous soaps, but these remain dispersed in the solution and do not deposit on hard surfaces or as colored spots dirty gray or a cheesy edge but in any case form a veil finely divided.

The following examples are aimed at clarify the invention, but without limiting it.

The base soap strips are dosed with the slurry and other components in a mixer usual soap (helical mixer with sieve with holes), it homogenize by several mixtures, transported to a press extrusion, it is cut and finished as usual in pieces.

Examples of base soaps

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one

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Examples of dye slurries

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Examples of soaps

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Examples of Combi bars

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Claims (7)

1. Soap product, shaped, which contains: a) one or more fatty acids with 12-22 atoms carbon in the form of its alkaline soaps, where acids Fatty are made up of 50-80% by weight of fatty acids from 16 to 18 carbon atoms, and 20-50% by weight of fatty acids of 12 to 14 carbon atoms, and b) one or more starch derivatives pregelatinized crosslinks, chosen from the group of esters of hydroxypropylated phosphate. 2. Preparation according to claim 1, characterized in that the starch diphosphate hydroxypropyl starch is used as the derivative of crosslinked starch, pregelatinized. 3. Soap product according to claim 1, characterized in that it additionally contains 5-30% by weight of free fatty acids with 12-22 carbon atoms. 4. Soap product according to claim 1, characterized in that it contains 20-50% by weight of amphoteric surfactants. 5. Soap product according to claim 1, characterized in that it contains 5-40% by weight of fatty acids with 12-22 carbon atoms, in the form of its alkaline soaps, in particular of a base soap, for example of a soap whose components are formed by sodium sebacate, sodium cocoate and salt of palm kernel fatty acids. 6. Soap product according to claim 1, characterized in that it contains water in an amount of 5-35% by weight. 7. Soap product according to claim 1, characterized in that it contains up to 15% by weight of synthetic, amphoteric, cationic, anionic, and / or non-ionic surfactants.