DE3145627A1 - METHOD FOR PERFUMING SOAPS, DETERGENTS AND COSMETIC PRODUCTS AND A PERFUME FOR CARRYING OUT THIS METHOD - Google Patents

Description

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SHIP ν. FÜNER STREHL SCHÜBEL-HOPF EBBINGHAUS FINCK

MARIAHILFPLATZ 2 * 3, MÖNCHEN SO POST ADDRESS: POST BOX 95 O1 6O ₁ D-8000 MUNICH Θ5

ALSO PROFESSIONAL REPWELSFT.NTATIVES UtIOBE 1ΗΓ IUROf- ¹ F-AN PATENT OFTICE

- / (- · KARL LUDWIG SCHIFF (1B64 -1978)

DIPL. CHEM. OR. ALEXANDER V. FÜNER OIPL. ING. PETER STREHL DtPL. CHEM. DR. URSULA SCHÜBEL-HOPF DIPL. INTO THE. DIETER EBBINGHAUS DR. ING. DIETER FINCK TELEPHONE (Ο8Θ) 4B2O54 TELEX 5-23 565 AURO D TELEGRAMS AUROMARCPAT MUNICH

Process for perfuming soaps, detergents and cosmetic products and a perfume for performing this method

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

The previously known processes for perfuming cosmetic products, detergents, in particular of liquid and pasty detergents, which are predominantly surfactants, water, dyes, perfumes and contain other additives, based on the direct dosage of a liquid perfume composition in the agent. In the majority of cases the perfume is added on its own, in exceptional cases also mixed with some further additions. The addition is followed by mixing and homogenizing with the bulk of the product. A disadvantage of this process is the fact that the perfume composition from the finished products released into the atmosphere through diffusion and volatilization and thereby their content during storage

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is reduced considerably. This reduction is particularly evident in the case of more volatile perfume compositions Noticeable in a very short time after production, with during the first four weeks the original perfume content is reduced by up to 20% by weight. Even with others, proportionately less volatile perfume compositions, even if after a longer period of time, one can approximately after six to eight months, a reduction in the original perfume content of up to 30% by weight can be observed.

A disadvantage of this manufacturing process is the fact that it takes a relatively short time Time after production deteriorate the usefulness of the products, which of various Must be stored for a long period of time before use.

Other known methods for perfuming soaps use to increase the stability of the perfume in the soap the addition of another substance, usually a powdery sorbent, for example the porous one hydrated silica as described in DT-PS No. 837,914. With this addition can be compared to the perfuming process already mentioned by sorption of the volatile perfume composition in the porous material a reduction in its volatility and thus an increase in stability the perfuming of the product, especially the Storage, achieve. However, this method is disadvantageous in that the sorption and desorption properties of the sorbent depend on the properties of the sorbed substance, in particular on the chemical Composition of the groups and bonds in the. physical, or physicochemical, while forces arising from the sorption process come into play. Because of the different chemical

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Composition of perfume compositions, which is a large mixture of different chemical substances represents the use of some sorbents is considerably limited.

Another disadvantage of this method of increasing the stability of the perfume in soaps is that it is not it is possible to automatically dose the powdered sorbent on some of today's technological devices, because of the arrangement of these devices for metering liquid components. Even after the patent mentioned the addition of hydrated silicon oxide with other components in the soap mass is admitted and in this way some available facilities are used However, another disadvantage of this method is that the perfume in the whole, containing the sorbent Soap mass is added, but this does not ensure that the entire perfume is exclusively on this Sorbent is sorbed and thus stabilized. You can even reduce the content of soaps made in this way observe the perfume in the product after storage. Especially with more volatile perfumes, it occurs during the first four weeks to a reduction in salary of an average of 15 to 20% by weight.

The use is also disclosed in US Pat. No. 4,209,412 of perfumes in detergents known in the form of particles which form a continuous polymeric matrix, in which the perfume droplets are unevenly dispersed with the help of an emulsifier. That way you get perfumed particles which not only have an immediate but also a long-term perfume effect. They consist of 30 to 70% by weight of a water-insoluble perfume and 25 to 65% by weight of a perfume in water soluble polymer and emulsifier. An analog

Par film carriers based on carboxymethyl cellulose are used, as is known from GB-PS 1 503 897. In both cases, a Process for the stabilization of perfumes with the help of water-soluble polymeric substances described, which enables are to form a solid gel containing the perfume. However, in order to achieve the desired effect the use of a relatively large amount of a water-soluble polymer required, so that the 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 in the Application in the product a relatively large amount of other substances is entered, which predominantly their functional properties are poor or not at all influence. It is also disadvantageous that the perfume, which is in principle stabilized by encapsulation is obtained in an independent manufacturing operation, which puts the cost on the perfuming of the detergents elevated. Another disadvantage lies in the behavior of the continuous polymeric matrix in aqueous media Systems, which the use of the perfume stabilized in this way only to some, for example powder shaped detergents where, in addition to the low moisture content, there is no mechanical stress and destruction of the stabilized perfume occurs when the product is perfumed. You can do this with the Do not exclude soap perfuming and making.

According to the above-mentioned British patent, the perfume stabilized in this way is not for perfuming determined by other products. As a final form, it represents an air freshener with a protracted one Perfume effect.

The above-mentioned disadvantages are eliminated by the process for perfuming soaps, detergents and cosmetics Products in which the perfume is added to the processed mass with simultaneous dosing of other additives is introduced, according to the present invention.

The principle of the invention is that a polymer based on hydrocarbons is used in the perfume or halogen derivatives of hydrocarbons or alcohols, their ethers or esters, or organic acids and their derivatives, or polysaccharides and their derivatives or a polymer with a heterogeneous chain and / or copolymers and terpolymers dissolves or swells from the specified monomers and, if appropriate, mixtures thereof, after which this is applied to them Way stabilized perfume at the same time with further additives in the processed mass in an amount of 0.3 to 6.0% by weight is added.

The perfume for performing the above procedure contains said polymers in an amount of 2 to 40 wt .-%, with the perfume the remainder forms up to 100% by weight, i.e. 60 to 98% by weight. It contains polyethylene and polypropylene as hydrocarbons or polystyrene with a melt flow index of 0.5 to 5 g / 10 min., as halogen derivatives of the hydrocarbons Polyvinyl chloride with a molecular weight of 20,000 to 210,000, as alcohols, their ethers and Ester, polyvinyl alcohol, polyphenylene oxide, polyvinyl acetate or polyethylene glycol with a molecular weight from 6000 to 320 000, as organic acids and their derivatives polyacrylic acid, polymethacrylic acid, Polymethyl methacrylate, polybutyl methacrylate with a molecular weight of 6,000 to 320,000 as a polymer with a heterogeneous chain with a linear structure a urea-formaldehyde, a melamino-formaldehyde resin, Rosin, carboxymethyl cellulose,

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as a copolymer vinylcholride and vinyl acetate with a molecular weight of 30,000 to 160,000, butyl methacrylate and methyl methacrylate with a molecular weight of 12,000 to 240,000 and an acrylonitrile-butadiene-styrene copolymer with a melt flow index of 5 to 20 g / min. The method according to the invention enables a soap mass with a fatty acid titer of 36 to 49 ⁰ C to be processed.

In the soaps, detergents and according to the invention cosmetic products the ability of the perfume composition is used to gradually sorb, to wet and convert the polymer into a swollen, gel-like to soluble form and thus to form structural, well-flowing systems with the perfume contained in the polymer. This creates education of a gel system that contains the perfume in its structure, which when in contact with the base the cosmetic product or with the surfactants odena'xt the soap mass includes the perfume component thus reducing their volatility and preventing possible chemical changes during storage. These advantages of the invention over the known Solutions underscores the fact that it is possible on the available operating facilities in an analogous manner, the perfume composition in the form of a readily pumpable liquid mixture, which contains the polymer contains as a component stabilizing the perfume, to be dosed. The properties of the liquid, if any the gel-like mixture of the perfume and the polymer enable their combination with others in the manufacture of cosmetic products, soaps, liquid and pasty detergents. additives used and their common dosage in the mass of the product. The properties of the mixture of the perfume with the polymer in the mass of those mentioned

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Products obtained with the manufacturing method according to the invention, allow the perfume composition to stabilize and maintain a high level Perfume content even after a long period of storage, which affects the usefulness of the product from the point of view the perfuming from boosts.

The perfume stabilized according to the invention uses the properties of the polymer or the mixture of polymers, which by homogenization with the perfume forms a gel to a solution and, due to the mutual interaction of these components, increases the stability of the perfume by significantly limiting its volatility and its durability against chemical changes due to the influence of substances contained in the soaps, cosmetic agents, liquid or pasty surfactants and detergents. With this method, a completely homogeneous distribution of the perfume composition in the mass of the products mentioned is achieved at the same time. The effect of the process for the production of soaps, detergents and cosmetic agents according to the invention enables the perfuming during manufacture to be reduced by up to 50% by weight and, after a longer storage time, the same or even a higher fragrance intensity of the product compared with the previously known products to achieve. Another positive phenomenon is the stabilization of the suspensions and emulsions in liquid and pasty forms of the products. Another important effect of the perfuming process according to the invention is that the polymer in a mixture with the perfume reduces ^{the titer of the fatty acids in the soap mass by up to 4 ° C} which is favorably reflected in the improvement of the processability and homogeneity of the soap and to increase it

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of quality and quality characteristics. The stabilizers mentioned not only bring about the actual fixing effect, but also act as plasticizers. This fact enables the processing of a soap mass of relatively lower quality from such fat batches in which the fatty acid titer is 45 to 47 ⁰ C higher than the usual required values, which are necessary from the point of view of the processability of the soap during production and its properties are. A significant reduction in the deformity of the soap in comparison with soaps produced from the same soap mass using the previously known methods also has a beneficial effect.

The soaps were evaluated in such a manner that the soap samples repeated those processes which they go through with normal use and the resulting cracks and crevices the surface were visually traced during the test a scoring scale with the help of photographic standards established for individual types of soap. The final number, which is the measure of the constancy of Soap against cracking can have a minimum value of 2 (the soap changes throughout the test their surface area is not) and have a maximum value of 10 (the soap disintegrates). The soaps with the content of Perfumes stabilized according to the invention showed a higher resistance to deformation and according to the point evaluation scale they always had values 1 to 2 lower than soaps with the unstabilized perfume.

The method according to the invention for perfuming soaps, detergents and cosmetic products is explained in more detail in the following examples.

Examples Example 1

I-Aethyl-i-alkylamidoethyl-2-alylimidazoline metasulfate was placed in a container containing 28.6% by weight of warm water added in an amount of 4.7% by weight. After mixing, it became 16.5% by weight of one Condensation product of stearic acid with an excess of diethanolamine in acetic acid added. After adding 10.4% by weight of water, the mixture was stirred and homogenized for 1 hour. By adding 39.3% by weight of water and mixing, the mixture was cooled and mixed with 0.5% by weight of a liquid mixture, which is the perfume and polystyrene having a molecular weight of 210,000 in a weight ratio of both Components of 1: 0.2 contained, added. The perfume level in the suspension softener remained after eight Months of storage unchanged, while maintaining the original intensity and character of the fragrance the perfume composition.

Example 2

Xn a batch of shaving cream, which 17 wt .-% stearin, 8% by weight glycerine, 1% by weight triethanolamine, 0.5% by weight Potassium hydroxide, 2/5% by weight of petroleum jelly, 1% by weight of lanolin oil, and 69.7% by weight of water became 0.3% by weight of one liquid mixture consisting of a perfume and a polymer based on the acrylonitrile-butadiene-styrene copolymer 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 character of the perfume remained after 8 months Storage of the product unchanged.

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Example 3

To a liquid suspending agent, consisting of 11.5% by weight sodium alkylarylsul & nate, 6.4% by weight soap, 22.4% by weight sodium triphosphate, 2.6% by weight oleic acid diethanolamide, 1.0% by weight coconut fatty acid monoethanolamide, 0.2% by weight formalin and 55.6% by weight water 0.3 wt .-% of a liquid mixture, consisting of a Pax-füm and a polymer based on the Polyvinyl chloride acetate with a molecular weight of 140,000 and with a weight ratio of both components of 1: 0.25 was added. A product was obtained in which the intensity 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 of water and 0.5% by weight of borax was added with 1% by weight of a liquid mixture containing a perfume and a polymer based on the acrylonitrile-butadiene-styrene copolymer 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, the intensity and the character of the perfume of the product remained unchanged.

The process according to the invention for perfuming soaps is illustrated in more detail in the following examples.

Example 5

In a conventional technological proceed η for the production of toilet soap were added to 95.995 wt .-% soap composition containing 79 wt .-% of fatty acids having a titre of 43.2 ⁰ C, in a mixing device 0.2 wt .-% of titanium white, 0, 8% by weight carboxymethyl cellulose ,. 1.0 wt%

Water, 0.005 wt .-% colorant and at 20 ⁰ C 3.0 wt .-% of a liquid mixture of a volatile perfume, based on the Geranylacetats, Terpinylacetats and Dekanols and a polymer on the basis of Acrylonitr.il-butadiene-styrene copolymer having 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 the two components being 1: 0.15. After mixing the soap mass with the additives, the mixture was processed further mechanically in a piling machine and in a soap extruder. After the usual punching, a completely homogeneous, plastic and solid soap was obtained in the whole mass, with very good washing effects, while maintaining the perfuming until the soap was completely consumed. The perfume content in the soap remained practically unchanged after 2 months of storage and after 8 months the loss was only 15% by weight, based on the original content.

The Fettsäuretiter decreased after the addition of the stabilized with the PoIymerisat Perfume 40.8 ⁰ C, which manifested itself by improving the soap plasticity. There was also an increase in the production capacity of the technological facility. At the same time there was an increase in the resistance to cracking of the soap surface during use. On the scoring scale, according to the method already described, the soap containing the polymer showed a value of 3.2, compared to the value of 4.4 which the same soap with a content of the same amount of the unstabilized perfume when evaluated with the same method exhibited.

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Example 6

A toilet soap was produced in the same way as in Example 5, but with one difference, that a liquid mixture of the perfume with a polymer based on a polyvinylcholride acetate with a molecular weight of 140,000 was used, in the weight ratio of the two components was 1: 0.25 and the viscosity was 1.06 Pa s. One received Toilet soap with the same properties and with the same perfume stability in storage as in the example 5. The decrease in the perfume content after 8 months Storage was a mere 17% by weight based on the original salary.

Example 7

In a common technological process on a continuous plant for toilet soap production was in the soap mass, which contained 80 wt .-% fatty acids with a titre of 46.8 ⁰ C, gradually a liquid suspension of 60 wt .-% of a mixture of one less volatile perfume based on linolylacetate, anisaldehyde, benzyl acetate and geraniol with a polymer based on an acrylonitrile-butadiene-styrene copolymer with a melt flow index of 16 g / 10 min., in which the weight ratio of the two components was 1: 0.12, 2.5% by weight of titanium white, 1.5% by weight of nitrile acetic acid sodium salt and 36% by weight of water are metered in. The dosage of the liquid suspension was chosen so that the weight ratio ni s xu of the soap mass was 2:98. After homogenization in a mixing and homogenization tray and after further preparatory work, 1 " ¹ mg of the mass obtained in soap extrusions and after punching, a toilet soap with the same properties as in Example 5 was obtained and the perfume loss after 8 months of storage was only 8% by weight. %,

based on the original quantity. The Fettsäuretiter dropped to 42.3 ⁰ C. The cracking of the soap had 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 way as in Rr ί game 7 a wcilcrt ¹ ToileLtenseif CM) HOi te produced, but with the difference that the liquid suspension is a mixture of the perfume with a polymer based on polyvinyl acetate with a molecular weight of 120,000 which the weight ratio of the two components was 1: 0.20. A toilet soap was obtained with the same properties as in Example 7, the loss of perfume after 6 months of storage being only 7% by weight, based on the original content.

Example 9

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

Example 10

Granulated polystyrene with a molecular weight of 170,000 was used in an amount of 10% by weight. under ylctigern Stirring with 90% by weight of a perfume composition based on eucalyptus oil p-methyl benzoate, methyl hexyl ketone, Terpinol acetate, diethyl phthalate and L.imonon

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mixed. A liquid, homogeneous one was obtained stabilized perfume with the characteristic scent of the original perfume, its character, as well the intensity remained unchanged even after 12 months of storage.

Example 11

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

Example 12

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

Claims (8)

■ ': -:: 3H5627 PAT EJN TA JJWALTT E; _ SHIP ν. FUNER STREHL SCHÜBEL-HOPF EBBINGHAUS FINCK MARIAHILFPLATZ 2 * 3, MUNICH ΘΟ POSTAL ADDRESS: POST BOX 90 O1 6O, D-8000 MÖNCHEN 96 AS PROFESSIONAL REPRESENTATIVE BEFORE THE EUROPEAN PATENT OFFICE KARL LUDWIS. CHEM. DR. ALEXANDER V. FÜNER DIPL. ING. PETER STREHL DIPL. CHEM. DR. URSULA SCHÜBEL-HOPF DIPL. ING. DIETER EBBINGHAUS DR. ING. DIETER FlNCK TELEFON (ΟΒΘ) 4B2O54 TELEX 6-5S665 AUHO D TELEGRAMS AUROMARCPAT MUNICH DEA-22374 claims 1. A method for perfuming 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 de ren derivatives, polysaccharides and their derivatives and / or copolymers and terpolymers formed from the above monomers and optionally triggers mixtures thereof or allowed to swell, followed by the stabilized in this way perfume simultaneously with further additives are added to the processed mass in an amount of 0.3 to 6.0% by weight. 2. Perfume for performing the method according to claim 1, characterized in that there are polymers in an amount of 2 to 40 wt .-% and the Contains perfume in an amount of 60 to 98% by weight. 01 3H5627 SHIP ν. FQNER STREHL SCHOBEL-HOPF EBBINSHAUS FINCK 3. Perfume according to claim 2, characterized in that it is the polymer hydrocarbons, for example polyethylene, and / or polypropylene and / or polystyrene. 4. Perfume according to claim 2, characterized in that it is the polymer hydrocarbon halogen derivatives, for example contains polyvinyl chloride. 5. Perfume according to claim 2, characterized in that g e k e η η TO distinguishes that alcohols, their ethers and esters, for example polyvinyl alcohol, Polyphenylene oxide, polyvinyl acetate or polyethylene glycol contains. 6. Perfume according to claim 2, characterized in that g e k e η η - distinguishes that it contains organic acids and their derivatives, for example polyacrylic and / or polymethacrylic acid and / or polymethyl methacrylate and / or polybutyl methacrylate. 7. Perfume according to claim 2, characterized in that g e k e η η - draws that the polymer is a polymer with a heterogeneous chain with a linear structure forms, for example a urea-formaldehyde and / or melamino-formaldehyde resin and / or carboxymethyl cellulose and contains rosin. 8. Perfume according to claim 2, characterized in that it is a vinyl chloride-vinyl acetate copolymer as the polymer and / or a butyl methacrylate-methyl methacrylate copolymer or an acrylonitrile-butadiene Contains styrene copolymer.