EP0401331A1

EP0401331A1 - Cosmetic raw material consisting of cereal glue

Info

Publication number: EP0401331A1
Application number: EP90900100A
Authority: EP
Inventors: Dieter Braun; Ernst STEINBÖCK
Original assignee: Dragoco Gerberding and Co GmbH
Current assignee: Dragoco Gerberding and Co GmbH
Priority date: 1988-11-18
Filing date: 1989-11-17
Publication date: 1990-12-12
Also published as: WO1990005521A1; JPH03503169A

Abstract

Sont décrites la fabrication et l'utilisation de matières premières de cosmétique constituées de colle d'origine céréalière, notamment de froment. Les produits de ce type sont des substances biologiques dont l'emploi en cosmétique est nettement préféré aux produits synthétiques comme les divers polymères synthétiques utilisés notamment pour le traitement capillaire.The manufacture and use of cosmetic raw materials consisting of glue of cereal origin, in particular wheat, are described. Products of this type are biological substances whose use in cosmetics is much preferred to synthetic products such as the various synthetic polymers used in particular for hair treatment.

Description

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Cosmetic raw material made from cereal glue

The present invention relates to a method for producing cosmetic raw materials from cereal glue, in particular from wheat glue, and the use thereof.

Products of this type are biological substances whose use in cosmetics is clearly preferred over all synthetic products, such as the various synthetic polymers used in particular for hair treatment. However, it was previously not known that protein products can be obtained from cereal glue which are stable in cosmetic preparations and are soluble in an aqueous alcoholic medium with an alcohol content below 70% by weight. However, since the solvents for common cosmetic preparations are often based on these solvents or are even alcohol-free, there is a need for protein products that are soluble in such media, including aqueous media.

This object is achieved in that cereal glue is extracted in a first stage with a fat solvent and, after evaporating the extract, the extraction residue is extracted in a second stage with a polar, in particular water-containing solvent, preferably in the presence of small amounts of ammonia, and the protein mixture obtained in the process after separating the insoluble fractions from the solution by evaporating the solvent, leaving the residue and separating the excreted honey-like mass.

In order to produce the preferred product from vegetable glue, the cereal glue is, in a manner known per se, in a first process step with a fat solvent (e.g. Hexane), in particular, however, extracted relatively high-percentage alcohol and obtained a fat product from the solvent phase by evaporation in a yield of 0.5%. The extraction residue is then extracted in a second stage with a polar, in particular water-containing solvent (for example aqueous ethanol), preferably in the presence of small amounts of ammonia, a protein mixture dissolving which, after the insoluble constituents have been removed from the solution, by evaporating off the solvent , Leaving the residue and separating the excreted honey-like mass is obtained. Wheat glue, a protein-rich wheat flour fraction, is preferably used as the starting material for the product according to the invention. However, corn, barley, oats or rye can also be used in an analogous manner.

In the first extraction stage, ethanol, methanol, acetone (in each case in dry form) or cyclohexane is preferably used as the extraction agent. When using wheat glue, it is extracted, for example, with about six times the amount by weight of 96% ethanol.

The extraction in the first extraction stage is preferably carried out with stirring at an elevated temperature of about 40 ° C. for a period of 1-2 days, it being possible for this extraction to be repeated once or twice. The mass is then centrifuged and filtered.

It is even more favorable to carry out the extraction in the manner of a column chromatography, with the adhesive being slurried or poured into a column with filter soil and the solvent continuously passing through the mass.

The filtrate or eluate of this extraction stage is then evaporated under mild conditions at a temperature up to 40 ° C. by thin-layer evaporation in vacuo or by vacuum distillation.

If ethanol is used as an extractant in this step, a residue of ethanol may remain in the mass, the amount of which must be taken into account in the next extraction step. When using non-polar solvents, such as Ace ton or cyclohexane, care must be taken to ensure that these are evaporated before the next extraction step until they are solvent-free. The fat phase obtained in this way (gliastin absolute) is suitable in perfumes and aromas as a modifier with fixing properties or as a skin and hair care product. The gliastin absolu is protected against oxidation with 0.5% tocopherol aceate. It is preferably used in an amount of 0.5 to 1% by weight, based on the finished product. Subsequently, the residue from the first extraction stage is brought into solution in a second stage with aqueous organic solvent, for example 50-75, in particular 62-68% aqueous ethanol, a protein product which is dissolved after the insoluble material has been separated off Share, evaporating the alcohol and leaving the residue as honey-like mass.

The quantitative ratio of extractant to residue to be treated from the first extraction stage is preferably 6 to 6.5 to 1, the alcohol residue from the first process stage having to be taken into account.

The extraction of this second stage is preferably carried out in the presence of small amounts of ammonia, in particular an amount of 1 to 2% by weight, based on the extraction residue of the first stage.

To carry out this second extraction stage, the reaction components are advantageously mixed with one another and then left to stand for at least 12 hours.

After the insoluble constituents have been separated off in a first press while slowly increasing the pressure to 15 atm in the presscake, the solution obtained is treated with activated carbon or diatomaceous earth, filtered and freed from the alcohol under vacuum until it becomes cloudy. The remaining solution is, if necessary ter full vacuum, cooled and left to stand. A tough mass settles out; the water phase is discarded and the residue is adjusted to about 20% by weight with 96% ethanol, remaining alcohol also having to be taken into account.

Immediately after completion of this solution, it is adjusted to a pH of about 3.5 with o-phosphoric acid.

By adjusting the pH value to 3.5, the oxidation ability of the cysteine to cystine is reduced and the shelf life of the product is improved. Acidification does not result in hydrolysis.

The protein product can optionally also be separated from the extraction solution of the second stage by cooling the solution to about −20 ° C. or by diluting with distilled water in a ratio of about 1: 1 and leaving to stand at about + 2 ° C. to m ximal about 9 ° C can be obtained.

It has been shown that the nic extractable portion is always better to separate as a solid residue with increasing extraction time.

The lower the temperatures during the service life, the greater the amount of protein product yield obtained.

Alcohol (15 - 17%) and water are still present in the protein product. The protein content, based on the weight of the product obtained, is about 22%.

If the mass is then allowed to warm to room temperature, it becomes honey-like and clear. _

If cereals other than wheat gluten are used, the water additive must be adjusted to obtain a residue that is not too solid.

If desired, the protein product separated in this way can be freeze-dried and thereby obtained in solid form

The protein product obtained can be used as such or in hydrolysed form as a constituent of hair and skin care products.

Use: hair care 1 - 4% skin care 0.5 - 1%

The product is an extremely gently extracted extract of vegetable proteins in food purity. Due to its composition, this product, particularly with thin hair, can noticeably achieve more fullness and hold. The broad, nurturing effect is particularly evident from the aesthetic shine of the hair. The film applied to the hair has a dirt-repellent effect, which can extend the washing intervals. After the treatment, combability is excellent, with no static charge being noticeable.

Instructions for use and cosmetic properties: hair care (hair tonic, lotions, friction, shampoos), skin care (facial tonic, skin milk and shower bath), hair coloring (hair tinting gel, hair tinting lotion), The product gives the hair more fullness and hold and has a nourishing effect. The washing intervals are extended. Static charge reduction. Can also be used in barrier creams and in the food and pharmaceutical industries for chocolate and dragee varnishes, film formers for wound coverage.

Example 1 Production of a fat-free wheat gluten protein a) Separation of the fat portion from wheat glue

10 kg of wheat gluten are sprinkled into 60 kg of 96% ethanol with stirring and stirred at 40 ° C. for 1 to 2 days

After the liquid phase has been separated off by centrifuging and filtering, the filtrate is concentrated at a temperature up to 40 ° C. by means of vacuum distillation until the residue is largely solvent-free. Loot of fat product: about 460 g.

b) Preparation of the protein product from the extraction stand was from Example la

The centrifuge residue from example la is weighed, the non-separable ethanol residue is determined and taken into account for the further amounts of solvent.

The procedure is now as follows:

1. Suspend 12 kg of moist wheat gluten with approx. 50 kg of 96% ethanol (phase A).

2. Preparation of the aqueous component: 25 kg of water + 0.75 concentrated ammonia solution (25%) (phase B).

3. Phase B is mixed into phase A with stirring; the mixture is then stirred for at least 20 min.

4. Allow to stand for several hours. 5. The insoluble parts are pressed in a press. Yield: 74 kg (13.2 kg press cake = 1.5 kg loss of liquid).

6. 700 g of activated carbon or diatomaceous earth are added to the product solution; the mixture is heated to 40 ° C. and stirred for at least 3 days.

7. The solution from step 6 is filtered and ein¬ geengt _largely abgedampftist until the alcohol and a haze entries

After shutting off the steam supply and applying the full vacuum, the temperature is reduced to 10 ° C (approx. 15 minutes). The protein with the characteristic amino acid composition (l analysis) now fails. The final separation takes place after about 12 hours (room temperature) with the help of the separating funnel.

8. The wheat gluten protein precipitates as a honey-like syrup.

The water phase is discarded and the honey-like. Part is adjusted with ethanol (96%) to approx. 18% by weight ethanol - taking into account the residual alcohol.

9. The solution of step 8 is set with o-phosphoric acid ^'to pH 3.5; End product: approx. 50% with 22.5% protein and 20% alcohol.

Chemical-physical properties:

Appearance honey-like

Odor neutral

Moisture content approx. 78%

Protein content approx. 22% (of the extract) pH approx. 3.5 (direct)

Refractive index n ² ° approx.1.427

Germ count: opt. Rotation ^α2 °: - 19

Acid number: approx. 7 - 7.5

Ester number: approx.11.15

Ethanol content: approx. 18-20% by weight

Analysis of protein content ^• : Main bands in the molecular weight range between 28-46.0 Protein: 44.3% (extract) Protein: 22% (extract)

Amino acids mg / g extract mg / g extra

Aspartic acid 12.3 6.1

Threonine 10.1 5.0

Serine 19.1 9.5

Glutamic acid 154.8 - • 77.4

Proline 49.8 24.9

Glycine 7.4 3.7

Alanine 9.1 4.5

Valine 16.4 8.2

Cysteine 8.0 4.0

Methionine 6.2 '3.1

Iso-leucine 17.4 8.7

Leucine 14.7 7.3

Tyrosine 7.2 3.6

Phenylalanine 28.4 14.2

Histidine 9.9 5.0

Lysine 5.7 2.8

Arginine 15.6 7.8

Application examples Example 2: DAY CREAM

100.0

Heat phase A and phase B separately to approx. 75 ° C, pour phase B slowly into phase A, add phase C after emulsification at approx. 40 ° C, roll last. Example 3 NIGHT CREAM

Neo PCL self-emulsifying. W / ö 25.0 A isopropyl myristate 5.0 lanolin anhvdr. 4.0

Distilled water 58.2 B Neo Dragocid liquid 0.3 propylene glycol 5.0

C protein extract according to Example 1 2.0 perfume oil 0.5

100.0

Heat phase A and phase B separately to approx. 75 ° C, pour phase B slowly into phase A, add phase C at approx. 40 C, roll last.

Example 4 HAIR SHAMPOO

4a) Marlopon AT 50 40.0

Tego Betaine L7 4.0 protein extract according to Example 1 2.0

Tartaric acid 0.04

Neo Dragocid liquid 0.24 distilled water. 53.22 Perfume oil 0.50

4b) Marlopon AT 50 40.00

Amine oxide WS 35 3.00 protein extract according to Example 1 2.00

Tartaric acid 0.04

Neo Dragocid liquid 0.24 distilled water. 54.00 perfume oil 0 _r 50 4c) triaethanolamine salt of

A alkylbenzenesulfonic acid 5.0%

(e.g. Marlopon AT 50) protein extract according to Example 1 2.0%

B sodium lauryl ether sulfate (Hoechst) 33.0% oleic acid diaethanola id 2.0% z. . C e

Mix A, mix B in succession, stir in C. After adding and completely dissolving D, E, stir in slowly.

With the addition of Comperlan CD, the viscosity can be adjusted as desired.

Example 5 HAIR FASTENER (PUMP SPRAY)

5 - 8% wheat protein according to example 1

0.2% perfume oil ad 100 ethanol / water (35/65)

Example 6 HAIRSTYL GEL A 1.5% (up to 3%) xanthan gum 35.0% isoproanol

B 0.2% perfume oil

C 50.3% distilled water.

D 4.0% (up to 8%) of wheat protein according to Example 1

Mix A, dissolve B, add C slowly, stir in D at the end. The mixture can be colored if necessary. ,

7. HAIR TONING GEL

A 1.5% (up to 3%) xanthan gum 35.0% n-propanol

B 0.2% perfume oil

C 58.8% distilled water

D 0.5% DRAGOCO dye e.g. B. Chestnut 5/078625

E.g. black 5/078626 e.g. tobacco 5/078624 e.g. blond 5/078621

E 4.0% (up to 8%) wheat protein according to Example 1

Claims

»Claims

1. Process for the production of cosmetic raw materials from grain glue, in particular wheat glue, by

Extraction, characterized in that in a first process step the cereal glue with a largely anhydrous fat solvent such as hexane or 96% ethanol! extracted and a fat product is obtained from the extract by evaporation and that the extraction residue is then extracted in a second stage with a polar, in particular water-containing solvent, such as aqueous ethanol, preferably in the presence of small amounts of ammonia, a protein product going into solution after the insoluble constituents have been separated off from the solution, the alcohol is evaporated off, the residue is left to stand and the separated honey-like mass is separated off.

2. The method according to claim 1, characterized in that methanol, 96% ethanol, acetone or cyclohexane is used as the extractant in the first extraction stage.

3. The method according to claim 1 or 2, characterized in that the wheat glue is extracted with about 6 times the amount by weight of 96% ethanol.

4. The method according to any one of claims 1 to 3, characterized in that the extraction in the first

Extraction stage with stirring at an elevated temperature of about 40 ° C for a period of 1 to 2 days or by column extraction. _ ^ _

5. The method according to claim 1 to 4, characterized in that in the second extraction stage about 62-68%, in particular about 65% ethanol, in particular in a ratio of 6 to 6.5 parts by weight, based on 1 part . Part extraction residue of the first extraction stage is used.

6. The method according to claim 5, characterized in that the extraction of the second stage in the presence of small amounts of ammonia, preferably in an amount of 1 to 2 wt .-%, based on the extraction residue to be extracted from the first stage.

7. The method according to any one of claims 1 to 6, characterized in that the solution of the protein product is separated from the insoluble components after extraction, treated with activated carbon or diatomaceous earth and then the alcohol is partially separated by vacuum distillation.

8. The method according to any one of claims 5 to 7, characterized in that the solution of the proteins partially freed of alcohol, optionally under full vacuum, is cooled to a temperature of about 10 ° C and left until the protein has precipitated.

9. Use of the protein product obtained according to one of claims 1 and 5 to 8 as a constituent of cosmetic preparations.

10. Use of the protein product obtained according to one of claims 1 and 5 to 8 as a constituent of hair and skin care products.