DE3145627C2 - - Google Patents

Description

The invention relates to a method for perfuming of soaps, detergents and cosmetic products.

The previously known methods for perfuming cosmetic products, detergents, in particular of liquid and pasty detergents, which predominantly surfactants, water, dyes, perfume and contain further additions are based on the direct Dosage of a liquid perfume composition in the agent. The perfume becomes independent in the majority of cases added, exceptionally also mixed with some other additives. After adding, mixing follows and homogenizing with the bulk of the product. A disadvantage of this method is the fact that the perfume composition from the finished products through diffusion and volatilization into the atmosphere released and thereby their content during storage  is significantly reduced. This diminution is particularly useful for more volatile perfume composers sitions in a very short time after the manufacture noticeable during the first four weeks a reduction in the original perfume content up to by 20% by weight. Even with others, relationship moderately less volatile perfume compositions, even after a long period of time, approximately after six to eight months, a decrease in the original monitor perfume content up to 30% by weight. A disadvantage of this manufacturing process is the Fact that in a relatively short Time after manufacture the useful properties of the Deteriorate products that come from different Stored for a long time before use will.

Other known methods for perfuming soaps use to increase the stability of the perfume in the soap the addition of another substance, usually a powdered sorbent, for example porö hydrated silicon dioxide, as in the DT-PS No. 8 37 914 is described. With this addition can be compared to the perfume already mentioned process by sorption of the volatile perfume compositions tion in the porous material a reduction in their Volatility and thereby an increase in stability the perfuming of the product, in particular the Storage. However, this procedure is so far disadvantageous than the sorption and desorption properties properties of the sorbed Substance are dependent, especially on the chemical Composition of groups and bonds, which in the physical, or physico-chemical, while forces arising from the sorption process come. Because of the different chemical  Composition of the perfume compositions, which one large mixture of different chemical substances represents use on some sorbents considerably limited.

Another disadvantage of this stability method Increase in perfume in soaps is because it is not is possible on some today's technological a the powdered sorbent automatically to do sieren, because of the arrangement of these facilities for dosing liquid components. Even after the mentioned patent the addition of hydrated silicon oxide with other components in the soaps mass is added and in this way some ver available facilities are used however another disadvantage of this method is that that the perfume in the whole, containing the sorbent Soap is added, but this does not guarantee makes all the perfume on this one only Sorbent is sorbed and thus stabilized. Even at Soaps made in this way can have a decrease in content Observe the perfume in the product after storage. It occurs especially during more volatile perfumes in the first four weeks for a reduction in salary of on average by 15 to 20% by weight.

From US-PS No. 42 09 412 is also the use of perfumes in detergents in the form of particles knows which a continuous polymeric matrix bil the one in which the perfume drops with the help of an emulsifier are dispersed unevenly. This way you get perfumed particles, which are not just an immediate, but also have a long-lasting perfume effect. They do not consist of 30 to 70% by weight of one in water soluble perfume and from 25 to 65 wt .-% one in water soluble polymer and emulsifier. An analog one  Perfume carriers based on carboxy are used methyl cellulose, as be from GB-PS 15 03 897 be is known. In both cases, a is Process for stabilizing perfumes with the help of described water-soluble polymeric substances, which be a solid gel containing the perfume is capable of form. However, to achieve the desired effect the use of a relatively large amount of one water-soluble polymer required, so that Weight ratio of the perfume to the polymer is low and in the majority of cases is in the range of 0.5: 1 to 3: 1 moves. This means that together with the perfume stabilized in this way at Application in the product a relatively large Amount of other substances is entered, which over weighing their functional properties not or un influence favorably. It is also disadvantageous that the in principle perfume stabilized by encapsulation obtained in an independent manufacturing operation will what the cost of perfuming the detergent tien increased. Another disadvantage is behavior the continuous polymeric matrix in aqueous Systems, which means the use of the stabili in this way Perfumes only on some, for example powder shaped detergents limited where there is next to the minor Moisture content with no mechanical stress and destruction of the stabilized perfume in the perfume product comes. You can do this at the Do not rule out soap perfuming and manufacturing. According to the British patent mentioned above, this is perfume stabilized in this way does not become perfume determined by other products. It poses as Final form an air freshener with a protrahier th perfume effect.  

The method for eliminating the disadvantages mentioned Perfuming of soaps, detergents and cosmetic Products in which the perfume is processed in the Mass with simultaneous dosing of other additives is introduced according to the present invention. The principle of the invention is that in Perfume is a polymer based on hydrocarbons or halogenated derivatives of hydrocarbons or alcohol len, their ether or ester, or organic acids and their derivatives, or polysaccharides and their derivatives vate or a polymer with a heterogeneous chain and / or copolymers and terpolymers from the specified monomers and, if appropriate, their Mixes dissolve or swell, after which it is applied to the This way, perfume stabilized at the same time as others Additions to the processed mass in an amount of Adds 0.3 to 6.0 wt .-%.

The perfume to carry out the ver fahrens contains the polymers mentioned in one Amount of 2 to 40 wt .-%, the perfume the rest forms up to 100 wt .-%, ie 60 to 98 wt .-%. As Hydrocarbons it contains polyethylene, polypropylene or polystyrene with a melt flow index of 0.5 up to 5 g / 10 min, as halogen derivatives of hydrocarbons substances polyvinyl chloride with a molecular weight of 20,000 to 210,000, as alcohols, their ethers and Esters, polyvinyl alcohol, polyphenylene oxide, polyvinyl acetate or polyethylene glycol with a molecular weight important from 6000 to 320 000, as organic acids and their derivatives polyacrylic acid, polymethacrylic acid, Polymethyl methacrylate, polybutyl methacrylate with one Molecular weight from 6000 to 320,000, as a poly merisat with a heterogeneous chain with a linear Structure of a urea-formaldehyde, a melamino Formaldehyde resin, rosin, carboxymethyl cellulose,  as a copolymer of vinyl chloride and vinyl acetate with a molecular weight of 30,000 to 160,000, Butyl methacrylate and methyl methacrylate with one mo molecular weight from 12,000 to 240,000 and an acryloni tril-butadiene-styrene copolymer with a melt flow index from 5 to 20 g / min. The Ver driving allows a soap mass with a fat to process acid titers from 36 to 49 ° C.

In the soaps, detergents and cosmetic products, the ability of Par film composition gradually takes advantage of sorbia Ren, to wet and the polymer in a swollen, convert gel-like to soluble form and thus structural, well flowing systems with that in polymer to form sat perfume. Thereby the bil of a gel system that is structured contains the perfume which when in contact with the ground location of the cosmetic product or with the surfactants or includes the perfume component with the soap mass and thus reduces their volatility and possible che prevents mixed changes during storage. These advantages of the invention over the known Solutions underlines the fact that it is possible on the available operating facilities analogously the perfume composition in the form of a easily pumpable liquid mixture containing the polymer as a component stabilizing the perfume, to dose. The properties of the liquid, given in the case of the gel-like mixture of the perfume and the poly merisats allow you to combine them with others the production of cosmetic products, soaps, liquid and pasty detergents used Additives and their common dosage in the mass of the product. The properties of the mixture of Perfumes with the polymer in the bulk of the above  Products obtained with the Her according to the invention positioning procedures, enable the stabilization of the Perfume composition and maintaining a high Perfume content even after a long storage period, what the usefulness of the product from the state point of perfuming increases.

The perfume stabilized according to the invention uses the Properties of the polymer or mixture of Polymers from which by homogenization with the Perfume a gel until a solution forms and as a result of mutual interaction of these components Stability of the perfume is increased by the fact that its perfume activity is significantly limited and its durability chemical changes due to the influence of Soaps, cosmetic products, liquid or pasty substances containing surfactants and detergents elevated. With this procedure, one becomes full at the same time homogeneous distribution of the perfume composition in the Mass of the products mentioned. The effect of Process for the production of soaps according to the invention, Detergents and cosmetic products enables Perfuming in manufacturing up to 50% by weight reduce and thereby after a longer storage period the same or even a higher fragrance intensity of the Product compared to the previously known Er to obtain certificates. Another positive move stabilization of the suspensions and Emulsions in liquid and pasty forms of Products. Another significant effect of Perfume method according to the invention is that the polymer mixed with the perfume the titer reduces fatty acids in the soap mass by up to 4 ° C, which is beneficial in improving workability and reflecting homogeneity of the soap and increasing  of quality and quality characteristics. The Stabilizers mentioned do not only cause the actual fixation effect, but also act as Plasticizers. This fact enables Processing a soap mass of proportionate lower quality from such fat deposits, at which the fatty acid titer is 45 to 47 ° C higher than it corresponds to the commonly required values, which from the standpoint of workability of the soap at the Manufacturing and their properties are necessary. Also a significant reduction in the malformation of the Soap compared with the same soap mass with the previously known method makes soaps felt itself favorably.

The soaps were rated in such a way who repeats the soap samples to those processes which they have been subjected to in normal use go through and the resulting crevices and cracks the surface was visually checked during the test a point rating scale using photographic standards developed for individual types of soap. The final number, which is the measure of the constancy of the Soap against cracking can be a minimum worth 2 (the soap changes throughout the test their surface not) and a maximum of 10 (the Soap disintegrates). The soaps containing Perfumes stabilized according to the invention showed a higher resistance to malformation and after the point rating scale they always showed 1 to 2 lower people as soaps with the unstabilized perfume.

The inventive method for perfuming Soaps, detergents and cosmetic products explained in more detail in the following examples.  

Examples example 1

In a container containing 28.6% by weight of warm Water, became 1-ethyl-1-alkylamidoethyl-2-alylimida zolin tetasulfate in an amount of 4.7 wt .-% added give. After mixing, 16.5% by weight became one Condensation product of stearic acid with a Excess diethanolamine added in acetic acid. After adding 10.4 wt% water, the mixture Stirred for 1 hour and homogenized. By adding 39.3% by weight of water and mixing became the mixture cooled and with 0.5% by weight of a liquid mixture, which is the perfume and polystyrene with a molecular weight of 210,000 in a weight ratio of both Contained components of 1: 0.2, added. The perfume The leveling agent in the suspension remained after eight Months of storage unchanged, while maintaining the original intensity and character of the fragrance the perfume composition.

Example 2

In a batch of shaving cream, which contains 17% by weight of stearin, 8% by weight glycerin, 1% by weight triethanolamine, 0.5% by weight Potassium hydroxide, 2.5% vaseline oil, 1% lanolin oil and 69.7% by weight of water, 0.3% by weight became one liquid mixture consisting of a perfume and a polymer based on the Acryloni copolymer tril-butadiene-styrene with a melt flow index of 16 g / 10 min and with a weight ratio of both Components of 1: 0.12 added. The intensity and the character of the perfume remained after 8 months Storage of the product unchanged.  

Example 3

To a liquid suspension medium consisting of 11.5% by weight sodium alkylaryl sulfonate, 6.4% by weight soap, 22.4% by weight sodium triphosphate, 2.6% by weight oleic acid di ethanolamide, 1.0% by weight coconut fatty acid monoethanolamide, 0.2 wt% formalin and 55.6 wt% water 0.3% by weight of a liquid mixture consisting of a perfume and a polymer based on Polyvinyl chloride acetate with a molecular weight of 140,000 and with a weight ratio of both components of 1: 0.25. It became a product get the intensity after 8 months of storage and the character of the fragrance remained unchanged.

Example 4

A skin cream consisting of 10% by weight beeswax, 67% by weight of almond oil, 9.5% by weight of cetaceum, 12% by weight Water and 0.5 wt .-% borax, was added with 1% by weight of a liquid mixture containing a perfume and a polymer based on the copolymer Acry ionitrile-butadiene-styrene with a melt flow index of 18 g / 10 min and with a weight ratio of both Components of 1: 0.15, mixed thoroughly. After 8 months Storage remained the intensity and character of the Perfume of the product unchanged.

The inventive method for perfuming silk fen is illustrated in more detail in the following examples.

Example 5

In a common technological process for manufacturing position of toilet soap was 95.995 wt .-% Soap composition containing 79% by weight of fatty acids with a Titer of 43.2 ° C, in a mixing device 0.2% by weight Titanium white, 0.8% by weight carboxymethyl cellulose, 1.0% by weight  Water, 0.005% by weight of dye and at 20 ° C 3.0% by weight of a liquid mixture of a volatile perfume Basis of geranyl acetate, terpinylacetate and decanol and a polymer based on acrylonitrile-Bu tadiene-styrene copolymer with a melt flow index of 16 g / 10 min, with a viscosity of the perfume Polymer solution of 0.92 Pa s, the weight ratio of both components was 1: 0.15. After mixing the soap mass with the additives the mixture continues mechanically in a piling machine and processed in a soap extruder. After usual Punching became completely homo-wide preserved, plastic and strong soap, with very good Washing effects, while maintaining perfume until the soap is completely used. The perfume content in the soap remained practical after 2 months of storage table unchanged and after 8 months the loss was only 15% by weight based on the original content.

The fatty acid titer dropped after adding the poly merisat stabilized perfumes at 40.8 ° C, which is made noticeable by improving soap plasticity. There was also an increase in the production capacity of the technological facility. At the same time it came to the Stei resistance to cracking on the top of the soap surface during use. In the point scoring scale, according to the method already described, showed the soap containing the polymer has a value of 3.2, versus the value of 4.4, which same Soap containing the same amount of not stabilized perfumes when evaluated with the same Showed method.  

Example 6

In the same manner as in Example 5, one was Toilet soap made, but with the difference that a liquid mixture of the perfume with a poly merisat based on a polyvinylchloride acetate a molecular weight of 140,000 was used in which the weight ratio of both components 1: 0.25 and the viscosity was 1.06 Pa s. You got one Toilet soap with the same properties and with the same perfume stability during storage as in the example 5. The reduction in perfume content after 8 months Storage was only 17 wt .-%, based on the original salary.

Example 7

With an ordinary technological process a continuous toilet facility Soap production was included in the soap mass, which 80 wt .-% fatty acids with a titer of 46.8 ° C ent kept, gradually a liquid suspension of 60 % By weight of a mixture of a less volatile Perfume based on linolylacetate, anisaldehyde, Benzylacetats and Geraniols with a polymer Basis of an acrylonitrile-butadiene-styrene copolymer with a melt flow index of 16 g / 10 min, in which the weight ratio of both components 1: 0.12 be wore, 2.5% by weight titanium white, 1.5% by weight nitrile vinegar acid sodium salt and 36 wt .-% water metered. The Dosage of the liquid suspension was chosen so that the weight ratio to the soap mass 2: 98 amounted to. After homogenization in a mixing and Homogenizing pelletizer and after further processing the mass obtained in soap extruders and after A toilet soap with the same properties was punched obtained as in Example 5 and the perfume lust after 8 months of storage was only 8% by weight,  based on the original quantity. The fatty acid titer dropped to 42.3 ° C. The soap cracked a value of 4.1, compared to the value of 5.3 at the same soap with a non-stabilized perfume.

Example 8

In the same manner as in Example 7, another was Made of toilet soap, but with the bottom decided that the liquid suspension is a mixture of Perfumes with a polymer based on polyvinyl acetate with a molecular weight of 120,000 in which the weight ratio of both components 1: 0.20 be wore, formed. You got a toilet soap with the same properties as in Example 7, with the Perfume loss after 6 months of storage only 7% by weight, based on the original salary.

Example 9

In the same way as in Example 5, a toilet was made Tenseife produced, but with the difference that a liquid mixture of a less volatile perfume with polystyrene with a molecular weight of 180,000 was used, wherein the polymer content 0.285 g / lg Mixture was. You received a toilet soap same properties as in Example 5, with the Perfume loss after 8 months of storage 2 to 2.5 times was lower than that in the same way, however soap produced without using the polymer.

Example 10

Granulated polystyrene with a molecular weight of 170,000 was in an amount of 10 wt .-% under ste agitation with 90 wt .-% of a perfume composition based on eucalyptus oil, p-methylbenzoate, methyl hexyl ketone, terpinol acetate, diethyl phthalate and limonene  mixed. A liquid homogeneous was obtained stabilized perfume with the characteristic fragrance of the original perfume, its character, as well the intensity remains unchanged even after 12 months of storage remained changes.

Example 11

An acylonitrile-butadiene-styrene copolymer with a melt flow index of 16 g / 10 min was in a quantity of 5% by weight with constant stirring Amyl salicylate mixed in an amount of 20 wt .-%. After formation of a highly viscous solution, the other components of the perfume composition, i.e. Anisaldehyde, geranium oil, coumarin, phenylethyl alcohol and lemon jelly enzate, in an amount of 75% by weight added. A liquid stabilized was obtained Perfume with the same stability properties long-term storage as in example 10.

Example 12

A molecular weight polyvinyl chloride acetate of 140,000 and with a vinyl acetate content in the Copolymer of 5 wt .-%, was in an amount of 8% by weight with 92% by weight of a perfume composition based of limonene, linoly acetate, geraniol, benzyl acetate and Eugenol completely mixed to form one liquid stabilized perfumes with the same properties as in example 10.

Claims (8)

1. A process for the perfuming of soaps, detergents and cosmetic products, in which the perfume is introduced into the processed mass with simultaneous metering of further additives, characterized in that a polymer based on hydrocarbons or halogen derivatives of hydrocarbons or alcohols is used in the perfume , their ethers and esters, or organic acids and their derivatives, polysaccharides and their derivatives and / or copolymers and terpolymers, formed from the monomers mentioned above and, if appropriate, their mixtures, or can be allowed to swell, after which the perfume stabilized in this way is simultaneously cured further additives in the processed mass in an amount of 0.3 to 6.0 wt .-% adds. 2. Perfume for performing the method according to claim 1, characterized in that it is poly merisate in an amount of 2 to 40 wt .-% and that Contains perfume in an amount of 60 to 98 wt .-%.   3. Perfume according to claim 2, characterized records that it as a polymer hydro substances, for example polyethylene, and / or poly propylene and / or polystyrene contains. 4. Perfume according to claim 2, characterized records that it as a polymer hydro Halogenated derivatives, for example polyvinyl chloride contains. 5. Perfume according to claim 2, characterized records that as a polymer alcohols, their ethers and esters, for example polyvinyl alcohol, Polyphenylene oxide, polyvinyl acetate or polyethylene contains glycol. 6. Perfume according to claim 2, characterized records that it is organic as a polymer Acids and their derivatives, for example polyacrylic and / or polymethacrylic acid and / or polymethylmeth Contains acrylate and / or polybutyl methacrylate. 7. Perfume according to claim 2, characterized records that it is a polymer as a polymer with a heterogeneous chain with a linear structure forms, for example a urea-formaldehyde and / or melamino formaldehyde resin and / or carboxy contains methyl cellulose and rosin. 8. Perfume according to claim 2, characterized records that it is a polymer as a vinyl chloride Vinyl acetate copolymer and / or a butyl methacrylate Methyl methacrylate copolymer or an acrylonitrile Contains butadiene-styrene copolymer.