DE2421638A1 - SKIN CARE AND SKIN PROTECTION PRODUCTS WITH A CONTENT OF SKIN MOISTURIZERS - Google Patents

Description

"Skin care and skin protection agents with a content of skin moisturizers"

The invention relates to skin care and skin protection agents a content of substituted or unsubstituted alkylenediamines containing hydroxyl groups or their Salts as skin moisturizers.

It is well known that, in addition to other factors, there are certain factors that contribute to the protective measures of healthy skin Hygroscopicity heard. Become the substances on which this hygroscopicity, as well as its ongoing restoration the skin due to environmental influences, such as repeated washing with strongly wetting and extracting substances, Chemical influences, removed from strong weather influences, changes occur in the horny layer, which can greatly reduce the protective effect of the skin against harmful environmental influences.

It was therefore the task of skin care and skin protection " To develop means through which the puncture ability of the skin is fully or intensified despite damaging environmental influences Dimensions are retained and, in the event of damage, the restoration of the cornea is effectively supported.

This object has been achieved by using skin care and skin protection agents based on conventional ingredients, such as emulsifiers, Fatty substances, plant extracts, solvents, fragrances, Thickeners, preservatives used with

509847/0966

Henkel & Cie GmbH

Sheet 2 to patent application D 4 918 patent department

a content of substituted or unsubstituted alkylenediamines containing hydroxyl groups or their Salts of the general formula

R ₁ R ₂ N - R ₃ - NR ₄ R ₅ ,

in which R ₁ , R ₂ , R ₄ and Rj. independently of one another represent hydrogen, "an alkyl group with 1-4 carbon atoms, a hydroxyalkyl or dihydroxyalkyl group with 1-4 carbon atoms, where Rj. and Rj. together also represent a saturated heterocyclic 5 - Or 6-ring, which can also contain another H heteroatom such as oxygen or nitrogen and / or can be substituted by an oxo or hydroxyalkyl group, and R can stand for an alkylene group with 2-4 carbon atoms, with the proviso that at least one of the radicals R ₁ , R ₂ , R 1, Ru and R 1 - contains one or more hydroxyl groups, in an amount of 1-20 percent by weight, preferably 3-10 percent by weight, based on the total agent.

These products to be used according to the invention are eminently suitable for reducing water retention Maintain or restore skin and thereby make the skin soft and flexible and fully functional to obtain.

The production of the invention as a skin moisturizer Compounds to be used can be made by generally known processes, for example by catalytic Reduction of the cyanoethylation products of primary or secondary hydroxyalkyl or dihydroxyalkyl substituted Amines, such as B. for 4- (3-aminopropyl) -l-piperazine ethanol in the American patent 3 101 338 (Ref. Chemical Abstracts Vol. 60, column 2915), or by alkylation of such

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Henkel & Cie GmbH

Sheet 3 to the patent application D H918 patent department

hydroxyalkyl or dihydroxyalkyl substituted amines with aziridines. There is another possibility for production in the implementation of suitable alkylenediamines with compounds containing oxirane rings such. B. ethylene oxide, propylene oxide or glycidol. In this way, 1 to η hydroxyalkyl or dihydroxyalkyl groups can be found in alkylenediamines with η nitrogen-hydrogen bonds introduced by suitable choice of the molar ratio of alkylenediamine to epoxide as reported by M. S. Malinowskii in the monograph "Epoxides and their Derivatives", Israel Program for Scientific Translations, Jerusalem I965 ». The compound 1,3-bis- (dimethylamine) -propanol-2 can can be obtained according to the aforementioned reference on page 229 by condensation of 1 mole of epichlorohydrin with 2 moles of dimethylamine.

Substituted or unsubstituted alkylenediamines containing hydroxyl groups to be used according to the invention are, for example, N- (2-hydroxyethyl) ethylenediamine, N- (2-hydroxypropyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine , N, N-bis (2-hydroxy-propyl) -ethylenediamine, N, N, N ', N -Tetrakis- (2-hydroxy-ethylJ-ethylenediamine, N, N, N ¹ , N'-tetrakis- (2-hydroxypropyl) ethylenediamine, N- (2-hydroxyethyl) -N- (2,3-dihydroxypropyl) ethylenediamine, N, N-bis- (2-hydroxyäthy 1) -N ', N' -bis - (2,3-dihydroxypropyl) ethylenediamine, 2- (2-hydroxyethyl-amino) -propylamine, 3- (2-hydroxyethyl-amino) -propylamine, 3- (bis- (2-hydroxyethyl) -amino) -propylamine , 1.- (3-Amino-propyl) - ¹ I- (2-hydroxyäthy 1) piperazine, 1- (3- (2-Hydroxyäthyl-amino) -propyl-) - 4- (2-hydroxyethyl) -piperazine, 4- (3- (2-Hydroxyethyl-amino) -propyl) -morpholine, N- (3- (2-Hydroxyethyl-amino) -propyl) -piperidine, N- (3- (bis) -2-hydroxyethyl-amino ) propyl) pyrrolidin-2-one, 1,3-diaminopropan-2-ol, 1,3-bis (dimethylamino) propan-2-ol, l-amino -3- (bis- (2-hydroxyethyl) amino) propan-2-ol. They are mainly used in skin care and skin protection products in the form of their salts,

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Henkel & Cie GmbH

Sheet H for patent application D 4 9 ₁ Q ' Patent Department

As salts of the substituted or unsubstituted ones containing hydroxyl groups listed above Alkylenediamines come, for example, the halides, in particular chlorides, sulfates, phosphates, acetates, lactates, Tartrates, Citrates, Glycolates, Oxalates, Pumarates, Succinates and Malates in question. The salts are preferably adjusted so that they have a pH of 6 in concentrated aqueous solution.

All of the aforementioned salts are colorless and odorless, completely stable products, which are excellent have physiological compatibility and have no adverse effects on the skin care products to which they are applied. and have skin protectants.

As skin care and skin protection agents, those by the addition of the hydroxyl groups to be used according to the invention substituted or unsubstituted alkylenediamines or their salts are particularly skin-care products Properties are given, are day creams, baby creams, night and nourishing creams, cleansing creams, skin protection creams, Glycerine creams, creams with special additives of animal and vegetable origin, sun protection creams and sunscreen emulsions, facial tonics, aftershave lotions. Familiarization with skin care and Skin protection agents can be made in a known manner by simply stirring in or dissolving. In addition to the invention substituted or unsubstituted alkylenediamines containing hydroxyl groups to be used or the salts thereof, the cosmetic preparations can contain the constituents usually present in them, such as z. B. emulsifiers, fatty substances, plant extracts, preservatives, Contains fragrances and solvents in conventional amounts.

Henkel & Cie GmbH

Sheet ς for the patent application D Il 01 ft

s tjiu patent department

The pH value of the skin care and skin protection agents can and will move in the range from acidic to neutral expediently adjusted to weakly acidic values around pH 6.

The following examples are intended to explain the subject matter of the invention in more detail without, however, restricting it thereto.

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Henkel & Cie GmbH

Sheet 6 to the patent application D ^ t 918 patent department

Examples

Of those to be used according to the invention as skin moisturizers, Substituted or unsubstituted alkylenediamines containing hydroxyl groups were The compounds listed below are subjected to the tests and used in formulations.

A) Ij- (3-aminopropyl) -l-piperazinoethanol

The product was according to the specifications of the American Patent 3,101,338 by reacting 1-Piperazinäthanol with acrylonitrile at 110 - 120 ⁰ C and obtained catalytic reduction of the obtained 4- (2-cyanoethyl) -l-piperazinäthanols at room temperature,

B) N- (3-aminopropyl) diethanolamine

The product was prepared analogously by reacting 1 mole of 1,3-diaminopropane with 2 moles of ethylene oxide the information from M. S. Malinovskii in the monograph "Epoxides and their Derivatives", "Israel Program for Scientific Translations ", Jerusalem I965.

C) N- (2-Hydroxyäthy.l) -äthylenediamine hydrochloride

The product was prepared analogously to the information provided by M.S. Malinovskii in the aforementioned monograph by converting ethylenediamine obtained with ethylene oxide and subsequent neutralization (pH 6) with HCl.

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Henkel & Cie GmbH

Sheet 7 for patent application D ^ 918 . Patent department

D) N- (2-hydroxypropyl) ethylenediamine hydrochloride

The product was produced analogously to the information provided by M. S. Malinovskii by reacting Ethylenediamine with propylene oxide and neutralization with HCl.

E) Ν, Ν, Ν ¹ , Ν ¹ -Tetrakis- (2-hydroxyethyl) -ethylenediamine

The product was obtained analogously to the information from MS Malinovskii by reacting 1 mol of ethylene diamine with ¹ l mol of ethylene oxide.

P) 1,3-bis (dimethylamine) propan-2-ol hydrochloride

The product was produced analogously to the information provided by M. S. Malinovskii by reacting Epichlorohydrin with 2 moles of dimethylamine and neutralization with HCl.

The favorable behavior of the compounds to be used according to the invention with regard to water absorbency and The water retention capacity was determined using the test methods described in more detail below.

The water absorption capacity was determined by measuring the increase in weight on storage at 100 % relative humidity for 48 hours in mg of water per 100 mg of substance.

The water retention capacity was determined by determining the residual water content of a sample moistened with 300 mg of water per 100 mg of substance after storage at 0 % relative humidity under a pressure of 12 Torr for a period of k5 minutes, 11/2 hours and 8 hours as mg of water per 100 mg of substance. ''

The measured values listed in Table 1 below were obtained.

c η η ο / η ι π ο C

Sheet 8 for patent application D 4 918

Henkel & Cie GmbH

Table 1

Water retention and water absorption capacity of hydroxyl
group-containing, substituted or unsubstituted
Alkylenediamines Water retention in mg / 100 mg substance after 90 min. after 8 hours Water absorption in
mg / 100 mg of substance
after Ij 8 hours product after 45 min. 22nd 1} 195 A. 39 17th 7th . 17 * t B. 29 87 8th 371 C " 115 69 10 263 D. 109 32 II 213 E. 71 27 9 230 P. 85

The table above is next to the strong water absorbency also the considerable water retention capacity of the compounds to be used according to the invention and thus their good suitability as a skin-holding agent in skin care and skin care products Refer to skin protection agents.

Another test method was a method of determination the equilibrium moisture content, which is a measure of the water retention capacity and the determination of the water retention, Rehydration and elasticity of impregnated pig epidermis are used.

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INSPECTED

Henkel & Cie GmbH

Sheet 9 to patent application D 4918 patent department

1) Determination of the equilibrium moisture content

The substances to be examined (approx. 300 - 500 mg) were moistened with a defined amount of water • and at 23 ° C for 24 hours, different relative humidities (1 JS, '30 *, 47 5δ, 65 %, 89 % and 100 % relative) Moisture). The amount of water absorbed or released was determined gravimetrically and plotted graphically. From the resulting curves, conclusions can be drawn about the relative humidity at which neither water is released nor water is absorbed. This value, called equilibrium moisture, is a measure of the water retention capacity of a substance. The lower the value, the more positive the product is to be assessed.

2) Measurements on the pig epidermis

a) Obtaining the pig epidermis.

Immediately after the pigs have been killed, the bristles of the skin are cut off using a hair clipper (shaving head 0.1 mm). The pigs are scalded in 60 ° warm water for about 3-5 minutes, the epidermis • then peeled off and stored at -20 ⁰ C until use.

b) Determination of water retention and rehydration impregnated pig epidermis.

Punched pieces of epidermis (1x2 cm) were Bathed for 2 hours in a 10 percent solution of the test substance under standardized conditions using dabbed in a small press and hung freely between 2 clamps in a 100 ml Erlenmeyer-

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Henkel & Cie GmbH

Page 10 of the patent application D ij918 patent department

Flask dried at 23 ° C and 30 % relative humidity (adjusted by sulfuric acid-water mixtures). The desiccation of the impregnated sample to X% of the initial weight was compared with the corresponding value of the epidermis bathed only in water (blank value). The table shows the improvement in water retention and rehydration compared to the blank value in Δ% HpO. The deviations in the respective double tests were a maximum of - 2 absolute units. If there were major deviations, the experiment was repeated. The rehydration was achieved by drying the impregnated and swabbed pig epidermis ^{for 2 i i hours}

30 % relative humidity and subsequent 24-hour incubation at 90 % relative humidity determined analogously.

c) Elasticity measurements on impregnated pig epidermis

Punched out pieces of epidermis (1x6 cm) were bathed for 2 hours in 10% aqueous solution of the substance to be tested and dabbed under standardized conditions. The samples were incubated between 2 clamps at 75 % relative humidity and 90 % relative humidity for 24 hours and stretched in a Zwick tensile testing machine (type: 1402) at 0-50 ρ load. As a measure of the elasticity, the elongation was given in mm, which was ^{measured in the Hooke 1} area with a load between 5 - 30 ρ.

Those obtained in the tests described above Measured values can be found in Table 2 below.

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Tabel

Equilibrium moisture content and measured values Water retention '/ o HO 8th at 50 <7o r.h. 8th at the swine epid ermis at 75% r.h. Equilibrium after dehydration 0 Rehydration Δ "7 ° mm elongation between 5-30 ρ 0 product humidity (° / o r. F) at 30 ⁰ Io rH 23 Water absorption load 1.0 0 at 9 0 ° / o RH at 9 0 ⁰ J ₀ rH - 9 0 0.3-0.5 Blank value 47 14th 41 3.7 - A. 3 3.5 4.8 <7o A 14th ■ f- 5, 2 <fo 47 0 25th - Lactic acid 60 16 4.2 B. 4.6 ° h B. + 5.4% 60 18th Lactic acid

"-" not measured

The aforementioned measured values indicate the good suitability of the products to be used according to the invention as

Refer to humectant.

N) I fie

- * β Q

Henkel & Cie GmbH

Sheet 12 for patent application D 4918. · Patent Department

Below are some more examples of cosmetic Listed preparations which contain the substances to be used according to the invention as skin moisturizers.

Day cream weakly greasy

Fatty acid partial glyceride Cutina MD ^v

Dehydag 6.0 parts by weight

Stearic Acid _: 8.0 "

Mixture of non-ionic emulsifiers

Eumulgin C 700 ^ ^R * Dehydag 2 Octyldodecanol Vegetable Oil Paraffin Oil Triethanolamine 1,2-Propylene Glycol Product A Nipagin M Perfume Oil Water

Baby cream

3.0 π 4.0 Il 3.0 It 5.0 dd 0.4 Il 3.0 Il 3.0 Il 0.2 It 1.0 Il 63.4 Il

Mixture of higher molecular weight esters, mainly mixed esters

Pentaerythritol fatty acid ester and citric acid fatty alcohol

ester Dehymuls E ^v 'Dehydag 7.0 parts by weight

oleic acid decyl ester Vaseline Wool fat boric acid talc zinc oxide nipagin M product B water

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10.0 Il 10.0 Il 5.0 Il 0.2 Il 12.0 It 8.0 Il 0.2 It 5.0 It 42.6 ti

Sheet 13 for patent application D 4 918

• Night cream

Henkel & Cie GmbH

Patent department

242Ί638

Colloidal mixture of 90 10.0 Parts by weight Share cetostearyl alcohol and 12.0 ti 10 parts of sodium lauryl sulfate 7.0 It 2-octyldodecanol 2.0 Il Vegetable oil 1.0 Il Wool fat 5.0 It Glycerin 0.2 It Product C 1.0 It Nipagin M. 61.8 It Perfume oil water Boron Glycerin Cream Colloidal mixture of 90 12.0 Parts by weight Share cetostearyl alcohol and 8.0 It 10 parts of sodium lauryl sulfate 5.0 Il 2 octyldodecanol 2.0 It Vegetable oil 28.0 Il Boric acid 0.2 It Glycerin 3.0 Il Nipagin M. 111.8 It Product D water Sunscreen 30.0 Parts by weight Mixture of higher molecular weight esters 15.0 Il with fatty substances Dehymuls K * ^R * Dehydag 5.0 Il oleic acid decyl ester 0.2 It Light protection agent 3.0 dd Nipagin M. 46.8 It Products water

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Sheet 14 for patent application D

-Face mask

Mixture of fatty acid partial

glyceride with emulsifiers Cutina

LE ^(R) Dehydag

oleic acid decyl ester

Vitamin oil

kaolin

Rice starch

Nipagin M.

Product F

water

Henkel & Cie GmbH

Patent department

12.0 Parts by weight Ü, 0 dd 5.0 Il 2.0 dd 3.0 It 0.2 It 6.0 dd

67.8

aftershave

Oleyl cetyl alcohol

Ethanol 96 %

menthol

Fighter

Balsam of Peru

Perfume

Hammamise tract

Boric acid

Product B

Product F

water

Facial toner

Cucumber Juice Citric Acid Ethanol 96? Ig Product A fragrance water

1.0 Parts by weight 67.5 Il 0.2 Il 0.2 It 0.1 It 0.5 Il 10.0 It 0.5 It 5.0 dd 5.0 It 10.0 It

15.0 Parts by weight 0.2 Il 15.0 It 10.0 dd 1.0 Il 58.8 Il

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Henkel & Cie GmbH

Sheet j. 5 for patent application D 1} 918 Palentabteilung

Instead of those mentioned in the above recipes Compounds to be used according to the invention can also be other of those listed according to the invention with equally good success products to be used.

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Claims (4)

Claims in which R ₁ , Rp, R ₄ and R ₅ independently represent hydrogen, an alkyl group with 1-4 carbon atoms, a hydroxyalkyl or dihydroxyalkyl group with 1-4 carbon atoms, where R ₁ , and R, also together represent a saturated heterocyclic 5- or 6-ring, which can also contain a further heteroatom such as oxygen or nitrogen and / or be substituted by an oxo or hydroxyalkyl group, and R, can stand for an alkylene group with 2-4 carbon atoms, with the proviso that at least one of the radicals R ₁ , R _? , R ₃ , R ₄ and R ₅ contain one or more hydroxyl groups, in an amount of 1-20 percent by weight, preferably 3-10 percent by weight, based on the total agent. 2. skin care and skin protection agents according to claim 1, characterized in that they contain the hydroxyl groups, substituted or unsubstituted alkylenediamines in the form of their halides, in particular chlorides, Contain sulfates, phosphates, acetates, lactates, tartrates, citrates, glycolates, oxalates, fumarates, succinates and malates, - 17 - 509847/0966 Henkel & Cie GmbH Sheet IJ for patent application D 4918 patent department 3. Skin care and skin protection agents according to claim ^^ I and 2, characterized in that in addition to the hydroxyl groups acting as skin moisturizers containing, substituted or unsubstituted alkylenediamines or salts thereof common ingredients such as emulsifiers, fatty substances, Plant extracts, preservatives, fragrances, thickeners, solvents in the conventional Quantities included. 4. Skin care and skin protection agents according to claims 1-3, characterized in that their pH value is weak acidic values around pH 6 is adjusted. 509847/0966