DE2143122A1 - Means and procedures for strengthening fingernails - Google Patents

Description

813 Starnberg near Munich

DI PL-I N GK SI EB E RT G. G RÄTTI NGER Almeldaweg 12

Dipl.-Ing. DipI.-Wittech.-teg.
PATENT ADVOCATE

,,. ,, ^ .... Telephone (0 8151) 2730 and 4115

PATENT Attorney Dp!, Ln ₃ . Dipl.-Whfcch.-Ig Postecheckkonto Munich 66917

the

Attorney file 5149/1

General Chemicals and Cosmetics Limited, Sassoon House, Shirley Street, Nassau (Bahamas)

Means and procedures for strengthening fingernails

sszsssssacsssssssiasssss

Addendum to patent ... (patent application P 20 4J 612.8)

The invention relates to a method for the treatment of tissue and keratinhaltigea agents for use in this process; The invention relates specifically to substances and methods for increasing the resistance of keratinous tissue of the epidermis, including human nails, to cracking, splitting, breaking, hot, etc.

According to an older proposal (patent application F 20 4-3 612.8) is stated like the KoHagen-derived Polypeptides suspended or in lower aliphatic alcohols with preferably 1 to 3 carbon atoms, or in solutions of the alcohols mentioned in water, preferably with a solution content of 0.1 to 20 Percent by weight, can be solved. The polypeptides can be derived from koBagen-containing Proteins by splitting them into products with a MoIe

209828/1032

2U3122

gross weight from 500 to 2000; However, microcrystalline KoBagens of considerably higher levels can also be used. Molecular weight (e.g. about 300,000) can be used. Higher molecular weight protein derivatives, for example represented by the microcrystalline KoILagene, need not be used in concentrations as high as those of lower molecular weight. For these most materials it actually applies that they are more effective when viewed downwards, for example at 0.5 % , and are excellent fingernail preparations. In most cases it is not necessary to use concentrations above 2%.

According to the present invention, the polypeptide derivatives used in the fingernail active agents are used prepared by reaction of the free carboxyl and / or amino acid group or groups of the polypeptides with salt-forming reagents such as ammonia or a fatty acid. Suitable derivatives of the following type are im Commercially available: Polypeptide AAS, Polypeptide LSM, and Polypeptide 32 from Maywood Division of the Stepan Chemical Co., Maywood, New Jersey; Protein VSP-A200 from Wilson & Co., Inc., Allantoin Proteinate from Schuylkill Chemical Co., Philadelphia, Pennsylvania and SPP variety -AD of

- Croda, Ine *

Polypeptide AAS is a 100 % alcohol-soluble polypeptide derivative with a molecular weight of 500 to 2,500. Both the free amino and carboxyl groups react.

Polypeptide LSN and polypeptide 3? are ammonium and sodium po lypeptide salts. Both have an average molecular weight of 2,500.

209828/1062

2U3122

The protein WSP-A200 is also a 100 % alcohol-soluble compound, produced by a chemical reaction between polypeptides and fatty acids. The molecular weight is about 500.

Allantoin proteinate is produced by complexly combining allantoin with WSP X 1000 from Wilson at high temperatures.

SPP - variety AP is an alcohol-soluble protein; it is the condensation product of isostearic acid with polypeptides The product has a molecular weight close to 10,000.

Microcrystalline colloidal collagen is technically not to be regarded as a soluble polypeptide. The Avitene are examples of suitable commercially available microcrystalline coXagens manufactured by PMO Corporation, San Jose, California, by hydrolysis of Kd layers made from bovine hides with aqueous acids, tfie Hydrochloric acid, citric acid, or thioglycolic acid. This hydrolysis is continued until 10 percent by weight of the colagen are reduced to a colloidal submicron size. Avetene H is a collagen, which by aqueous hydrochloric acid is hydrolyzed. Avetene C is made by hydrolysis with citric acid. Avetene C is made by hydrolysis of fibrinogen. This is where the free carboxyl and / or amino groups go a reaction.

The miscibility in an alcoholic or aqueous carrier liquid to form a solution or suspension is an essential feature of the invention.

209828/1062

2H3122

Usually proteins are said to be alcohol-soluble if the protein is not contained in solid particles in the alcohol. By this definition, the polypeptide A AS is soluble ij $ s 100% anhydrous alcohol; peptides 37 and LSN are completely soluble up to a mixture of 60 % alcohol and 40 % water. In such a mixture, the solubility of the polypeptide derivatives drops sharply with the increase in the alcohol content from 60 to 95% up to the point where it is practically impossible in dehydrated alcohol.

VSP - X 250 is soluble up to 60% alcohol and its solubility can be improved by raising the pH value to approximately 7 _t 5r using ammonia. VSP-Σ 1000 and VSP-X 1000 C can be dissolved in aqueous alcohol with up to 50% alcohol.

In addition to their ability to promote rapid drying, alcohols also serve as preservatives. If the alcohol content rises to 17 to 20% or more, there is no need to use additional preservatives. '

Suitable alcohols include lower aliphatic alcohols having 1 to 6 carbon atoms, especially 1 up to 3 carbon atoms. The use of butanol, pentanol and hexanol is possible, but these alcohols evaporate more slowly than alcohols with 3 or fewer carbon atoms and are therefore fewer suitable as the most volatile solvents.

209828/1062

In a preferred embodiment of the invention, the 2-sheet polypeptide derivatives are used in an alcoholic or aqueous alcoholic solvent mixed with 0.1 to 20 percent by weight of one large-molecular polymeric resin, so that the overall mixture has better film-forming properties. An explanation for this effect may be found in the fact that the large molecules of the polymers and copolymers cover the nail surface like a partly occlusive means and thereby the loss of transso-aycholar Reduce humidity.

There are a variety of frames for use in the invention of commercially available resins. Some of such polymers and copolymers are as follows Table listed;

Table 1

link

Polyvinyl pyrrolidone

Polyvinyl pyrrolidone / vinyl acetate

Modified polyvinylpyrrolidone polyvinyl alcohol hydroxypropylmethyl cellulose

Alkyl monoester of polyvinyl vinyl ether / KaleinäureX

Trade name PVP / VA (GAF)

PVP / VA E 635 (GAF)

Ganex V-904 (GAF)
Elvanol 51-03 (Dupont) Methocel 60 HG 50 cps (Dow)

Gantrez ES-225 and Gantrez ES-425 (GAF)

209828/1062

Poly (methyl vinyl ether) Gantrez M (GAP)

Poly (ethyloxide) homo- Polyox WSH-1O and Polyox

polymer WSR-3O1 (union carbide)

Complex Calcium, Magnesium and Gum Aratic T ¹ T ¹ C Special AA Potassium salt of the polysaccharide USP (Tragacanth Importing

Corp.)

Arabinogalactan Polysaccharide Stractan AP // ·

(Stone hall)

Organophilic gum polysaccharide Gendriv 492 (General Mills) Sodium Carboxymethyl Cellulose ^ CMC 7 LP (Hercules)

Carboxylated polyvinyl acetate Resyn 26-1314 Copolymer (National Starch)

Carboxylated vinyl acetate fiesyn 28-2930 and Terpolymers Besyn 28-3307

(National Starch)

Acrylic copolymers COB 7000 and Dicrylan

325-50 (Ciba)

Acrylic resin Cerboset 525

(Β.Ϊ. Goodrich)

refined sodium Acrysol GS (Rohm & Haas)

Po Iy acryl at

The modified polyvinylpyrrolidone, as listed above, includes polyvinylpyrrolidone which is alkylated with various alpha olefins.

Examples of the invention are given below. In the examples, all parts and percentages are shown based on weight.

209828/1062

2H3122

Examples 1-18 describe the polymers and copolymers which are used in the fingernail strengthener according to of the invention can be used.

example 1
Material percent

Methocel 60 HG, 50 cps 0.5

Ethanol, 95% 58.3

Polyeptide AAS - 20 % solid in
Alcohol 10.0

Water 31 2

Clear, good film results.

The alcohol tolerance of a 20% solution of Methocel 60 Hg, 50 cps is 80%.

Example 2
Material Proaent

Klucel L 2.0

Ethanol, 95% 88.0

Polyeptide AAS - 20 % solid

in alcohol 10.0

Clear, good film results
Klucel can tolerate 100% alcohol.

Example 3
Material percent

Elvanol 51-03 2.0

Ethanol, 95% - 70.0

Water 18.0 Polyeptide AAS - 20% solids

209828/1062

2U3122

Clear, good film results.

Elvanol 51-05 can tolerate 80% alcohol if the concentration of Elvanol is 2 % .

Example 4

Ganex V-904 (GAF) - polyvinylpyrrilidone alkylated with alpha olefins.

Material percent

Ganex V-904 2.5

Xthanol, 95% 87-5

Polypeptide AAS - 20 % solid

in alcohol 10.0

Klare.lind good film results.

Ganex V-904 is soluble in 100% alcohol.

Example 5

Gantrez ES-225 (GAF) - ethyl monoester of poly (methyl vinyl ether / maleic acid). This is applicable to 50% solids in ethanol.

Material percent

Gantrez ES-225 1-5

Ethanol, 95% 85.5

Polypeptide AAS - 20 % solid
in alcohol 10.0

Good, poorly recognizable film results.

Gantrez ES-225 tolerates up to 100% alcohol.

209828/1 062

Example 6

Gantrez ES-225 - butyl monoester from Pcjjr (methyl vinyl ether / maleic acid). This is applicable to 50 % solids in ethanol.

The same results are achieved with Gantrez EES-A25 and Gantrez ES-225 and again their tolerance to alcohol is up to 100 %.

Example 7
Material percent

Gantrez M 1.5

Ethanol, 95% 88.5

Polypeptide AAS - 20% solid in
Alcohol 10.0

Good, faintly visible IP film results.

Gantrez H is alcoholic in all proportions

miscible.

Example 8
Material percent

Polyox WSE - 10 2.0

Ethanol, 95% 50.0

Water 33.0

Polypeptide AAS - 20 % solid

in alcohol 10.0

Good, recognizable film results.
The maximum amount of alcohol that a 2% solution of Polyox WSfi-10 can tolerate is 60 %.

209828/1 062

2U3122 - ίο -

Example 9
Material percent

Gum arabic 1.0

Ethanol, 95% 30.0

Water '59.0

Polypeptide AAS - 20 % solid
in alcohol *. 10.0

A good, clear film is formed.

Gum arabic is soluble in aqueous ethanol systems up to a limit of 60 % .

Example 10

Stractan AP ■ £ / - £., (Stein Hall) - Arabinogalactan polysaccharide.

Material percent

Stractan AP / ^ 2 2.0

Ethanol, 95% 30.0

Water 58.0 Polypeptide AAS - 20 % solids

in alcohol 10.0

Good, clear pilm results.

The alcohol content, which with Stractan AP ^.

is the same as that of

Gum arabic.

209828/1062

2U3122

Example 11
Material percent

Gendriv 492 0.1

Ethanol, 95 % 20.0

Water 69.9

Polypeptide AAS - 20 % solid

in alcohol 10.0

The film formed is good and clear.
A 0.1% solution of Gendriv 492 in water cannot tolerate more than 60% alcohol.

Example 12
Material percent

0.5

Ethanol, 95% 39.0

Water 59.5

Polypeptide AAS - 20 % solid

in alcohol 10.0

The film result is good.

The alcohol content of a low concentration of CM0-7LP can reach almost 50% alcohol.

Example 13

Material percent

Besyn 26-1314 1.0

Ethanol 95% 80.0

Water 9.0

Polypeptide AAS - 20 % solid in

Alcohol 209828/1062 ¹⁰ ' ⁰

Neutralized with AMPD (2-amino-2 methyl-1,3-propanediol) up to 90% of the neutralization value of Resyn 26-1314 which is 4,385 grammiAMPD per 100 grammes Resyn is 26-1314.

The film achieved is slightly hazy. Resyn 26-1314 is soluble in 100% alcohol. If lower concentrations of Resyn 26-1314 in ethanol are used than that 40% solids in the existing product, present, is a neutralizing one Funds such as AMPD required.

Example 14

The composition here corresponds to that in Example 13, except that Resyn replaces 26-1314 with Resyn 28-3307

The results of this composition are the same as for Resyn 26-1314.

The alcohol tolerance is again 100 % for this Resyn.

Example 15

COB-7000 (Ciba) - copolymer of acrylic ester and acrylamide. One of the monomers of the copolymer contains a basic tertiary amino group which is then neutralized with acetic acid. There are 20% solids in water and 5 % ethanol.

209828/1062

2H3122

- 13 -

Material percent

COB-7000 1.5

Ethanol, 95% 88.5

Polypeptide AAS - 20% solid

in alcohol 10.0

Adjustment of the pH value with AMPD to approximately 7

The 7Hk is weakly recognizable, but good. COB-7000 is soluble in 100% * alcohol.

Example 16

Dicrylan 325-50 (Oiba) - a polymer of acrylic esters, acrylamide, and acrylic acid salt. It is 50 % solid in ethanol.

Material percent

Dicrylan 325-50 1.5

Ethanol, 95% 88.5 polypeptide AAS - 20 % solid

in alcohol 10.0

The 3PiIm was weak and hazy.

Alcohol tolerance in the. Dicrylan 325-50 is included 100% alcohol.

209828/1062

2U3122

- 14 -

Example 17
Material percent

Carboset 525 2.5

Ethanol, 95 % 87.5

Polypeptide AAS - 20 % solid

in alcohol 10.0

The pH is determined by applying

AMPD (2-amino-2-methyl-1,3-propanediol)

set.

The film is faintly hazy, but good.

Carboset 525 is soluble in 100% alcohol.

Example 18
Material percent

Acrysol GSc 2.0

Ethanol, 95 % 20.0

Water 68.0

Polypeptide AAS - 20 % solid
in alcohol 10.0

The film is good, but slightly hazy.

The alcohol tolerance of Acrysol GS is 25%

The following Examples 19-26 describe the composition of fingernail strength agents using Polypeptides, polypeptide derivatives, microcrystalline KoUygen and mixtures of these substances.

209828/1062

In each case the remedy was applied _r by. Drip on and spread on fingernails where jeCifes was left to dry.

After one or two weeks of use, there were already significant improvements in the condition of the treated Fingernails.

In certain cases nail parts were cut off and collected and analyzed for hydroxyproline; such Analysis dint to show the presence of collagen compared to the keratin of the fingernail. These tests clearly showed a high concentration of hydroxyproline, which is absorbed by the treated fingernails became.

Example 19 material percent

Allantoin proteinate 2.0

PVP / VA E635 (polyvinylpyrrolidone / vinyl acetate, 50 % solid in ethanol) 2.5 ethanol, 95 % 10.0

Sorbic acid 0.1

Water 85.4

A good, clear film resulted.

A system with allantoin proteinate can absorb up to 20% alcohol.

209828/1 062

Example 20

Polypeptide LSN - 40 % effective in water. Material percent

Polypeptide LSN 10.0

PVP / VA E635 (polyvinyl pyrrolidone / vinyl acetate, 50 % solid in ethanol) 2.5 ethanol, 95% 25.0

Water best up to 100 %

The result was a clear, good film.

The alcohol tolerance is 35%.

Example 21

Polypeptides ^ 37 - 40% effective in water. Material percent

Polypeptide 4-37 10.0

Ethanol, 95% 25-0

PVP / VA E635 (polyvinylpyrrolidone / vinyl acetate, 50% solid in ethanol) 2.5 100% water best.

The old film was good and clear. The alcohol tolerance is 35 %.

Example 22 Croda SPP (g ^ acfei AD - 25% in alcohol.

209828/1 062

2U3122

Material percent

Croda SPP AD - 25 % in alcohol 10.0 PVP / VA E635 (polyvinyl pyrrolidone / vinyl acetate, 50 % solid in ethanol) 2.5 ethanol, 95% 87-5

The result was a clear, good film.

Croda SPP | gxa ^ e \ AD is in every alcohol ratio miscible.

Example 25

Polypeptide AAS - collagen polypeptide derivative up to 20 % effective in analydric ethanol.

Material percent

Polypeptide AlS 10.00 PVP / VA E635 (polyvinyl pyrrolidone /

Vinyl acetate, 50 % solid in ethanol) 2.00

Ethanol, 95 % 83.4-5

Water 5-00

Phenylsiloxane polymer 0.10

The purpose of using the phenylsiloxane polymer in the above composition, which is mixed in small amounts is to have a plasticizing effect.

It has been found that when using the according to Example 23 compound material in the usual way of

209828/1062

2U3122

Nails can be significantly improved in less than 2 weeks.

Example 24

Significantly advantageous results have been achieved with a substance of the following composition:

Material percent

Polypeptide ASS 10.00 PVPAA E635 (polyvinyl pyrrolidone /

. Vinyl acetate, 50% solid in ethanol 2.50

"Phenylmethylpolysiloxane 0.20

Ethyl alcohol, 95 % 87.20

Perfumes 0.05

Color order

A wide variety of combinations of polypeptides, microcrystalline KoJIagenen and polypeptide derivatives is possible to be used in finger nail strengtheners. If alcohol is used in the substance, care should be taken to ensure that it does not contain more alcohol is more than every single protein derivative can be tolerated.

Example 25

Material percent

Polypeptide AAS (20% effective polypeptide derivative in anhydridisehem Ethanol) 10.0

Protein WSF X250 (polypeptide
55 % in water) 5-0

209828/1062

2U3122

E635 (50 tf solid in ethanol)
(Polyvinylpyrrolidone / vinyl /
Acetate copolymer) 2.5

Sorbic acid 0.5

100% water best.

Example 26

Material percent

Lanasan CL (collagen polypeptide ^ 1.0 Polypeptide AAS (polypeptide descendant,

20 % in anhydride ethanol) 10.0

Elvanol 51-03 (polyvinyl alcohol) 2.5

Ithanol, 95% 52.0 water at 100%.

- patent claims -

209828/1062

Claims (1)

2H3122 Claims 1. Agents for treating keratinous tissue with polypeptides which are lower in aliphatic Alcohols or aqueous alcohols are present in the form of a suspension or solution, according to patent (Patent application P 20 43 612.8), characterized in that that a part of at least the polypeptides is in the form of a derivative which is formed by salt formation on the * Amino or carboxy group has arisen. 2. Agent according to claim 1, characterized in that the polypeptide is derived from collagen-containing raw materials by physical, chemical or enzymatic cleavage and that it has a molecular weight between 500 and 20,000. 3. Means according to claim 1, characterized in that the polypeptide comprises microcrystalline collagen | derived from collagen-containing raw materials and has a molecular weight between that of the collagen-containing fibers and the tropocollagen. 27 Aug 1971/645 20Θ828 / 1062