DE2217043A1 - SOAP, SHAMPOO AND AFTER SHAVE COMPOSITIONS WITH BACTERIOSTATIC PROPERTIES - Google Patents

Description

The present invention relates to soap, shampoo and aftershave formulations, those occurring in humans Kill microorganisms such as various pathogenic bacteria or prevent their growth. This highly antiseptic. Table formulations are made by using a relatively small amount of a 1,3-aliphatic diol and / or its mono- or diesters in connection with soaps, shampoos and aftershave lotions. The diols and diol esters impart certain soaps, shampoos, aftershave lotions and the like have antibacterial properties and replace them Substances like hexachlorophene.

There is a great need for soap and shampoo formulations, which have bacteriostatic properties. Usually the soap and shampoo formulations this property by using three main

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components, namely hexachlorophene, tribromosalicylanilide (TBS) and trichlorocarbanilide (TCC). Although If these formulations are satisfactory, the formulations of the present invention are superior to them they are effective against both gram-negative and gram-positive bacteria and are completely non-toxic for humans,

Normal soap is generally used in the antibacterial soap formulations of the present invention. As a rule, these soaps consist of a salt of a carboxylic acid with about 10 to 2.2 carbon atoms. The known soaps mainly consist of sodium salts of fatty acids with 12 to 18 carbon atoms. They are usually made by saponifying natural fats and oils with sodium hydroxide.

The main carboxylic acids for making soap are the naturally occurring fatty acids with 12 to 18 carbon atoms. These are straight chain acids with an even number of carbon atoms. These fatty acids occur in fats and oils as glycerol esters, i.e. as triglycerides. The main fatty acid components of the Common fats and oils used to make soap are: lauric and myristic acids from Coconut oil; Oleic and palmitic acids from palm oil; Oleic, palmitic and stearic acids from beef tallow; Olein-, PaI-mitin-, Stearic and linoleic acids from lard; Linoleic, oleic, and palmitic acids from cottonseed oil; Ricinoleic acid from Castor oil. In addition to the fatty acids, naphthenic acids, resin and tall oils are also used in the manufacture of soap used.

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The shaving creams according to the invention consist mainly of potassium stearate with minor amounts of sodium stearate and sodium and potassium coconut oil soaps. The main. requirement is a dense foam with sufficient strength to prop up the beard. This is characteristic of stearate foams. The potassium soap is because of the better Water solubility used. The shaving creams used in pressurized containers or aerosol contain triethanolamine stearate with a smaller amount of triethanolamine coconut oil soap. A stearate foam is also required here. The triethanolamine soaps are used because they are more water-soluble than even the potassium soaps.

The soap shampoos according to the invention generally consist of 15 to 20 % potassium coconut oil in water. This soap gives a clear solution at this and higher concentration. The sodium soaps are less soluble and the triethanol soaps add to the cost.

Scouring soaps generally consist of potassium soaps knock down low-quality oils such as soy or olive oil. The main consideration here is cost and good water solubility. Tall oil soaps are often used used. In general, soaps made from resin acids and unsaturated fatty acids are very soluble in water, and the foam is loose and watery. The cleaning power is satisfactory at room temperature, but at higher temperatures Temperatures lower than those of sebum soaps.

Potassium soaps or soft soaps, also called soft soaps, are usually made in warm processes

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(semiboiling process). The fat and the alkali solutions are heated together until saponification is complete. The soft soaps are not salted out. If sodium chloride were added, sodium soap and potassium chloride would be formed. Semi-heated Soaps (semiboiled soaps) retain all of the glycerine obtained during the saponification.

Toilet soaps are based on saponified natural fats, synthetic detergents, or both. In bars of soap, tallow is by far the most widely used raw material, followed by coconut oil. Other common carbon ions are palm, olive, peanut and palm kernel oils. ASTM regulations require a minimum anhydrous soap content of 62-83 % and a maximum free alkali gel (plus alkaline salt) of Z.3 % A typical formulation consists of:

Sodium soaps - a 87.0 %

Moisture - b 12.0 %

Perfume 0.9%

Preservative - ο 0.1 %

100.0 %

a - 15 to 25 % coconut oil, 75 to 85 % sebum;

b - "Personal Ivory" contains about 20 % water;

c - tin-II-chloride, tin-IV-chloride or EDTA.

In deodorant soaps, a small percentage of a bacteriostatic agent is added, such as 0.5 % hexachlorophene plus 0.5% TCC (3, k, k '-trichlorocarbanilide);

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0.5% diaphene (di- and tribromosalicylanilide) or 0.6 % each of TCC, fluoromethyl-TCC and diaphene.

Detergent bars are made with either synthetic detergents Made alone or in combination with soaps. Some typical formulations consist of:

Combination piece dry basis - a

soap 70.0 % Sodium coconut alcohol sulfate 20.0 % Coconut monoglyc eride sulfonate 10.0 % 100.0% TCC 0.6-b Diaphs 0.6-b Perfume 0.8-b

a - All pieces contain 8-10 % water; b - percent of the basic formulation.

Detergent Bar Dry Base - a

Igepon A 70.0 %

Stearic acid 30.0 56

100.0%

Perfume . 0.8-b

a - All pieces contain 8-10 % water; b - percent of the örund formulation

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Some soaps contain a color stabilizer such as stearic hydrazide in a concentration of 0.025-0.05 %.

There are many types and forms of suitable shampoos, depending on their physical form or in some cases can be classified according to their particular constituents or properties. There are liquid clear ones Shampoos, shampoos in the form of liquid creams or cream lotions, cream pastes, ice shampoos, herb shampoos, Dry shampoos, liquid dry shampoos, colored shampoos, and aerosol shampoos. In addition, one or more of these types are based on special raw materials, or have special additives with those from a certain Product antiseptic or anti-dandruff shampoos are made, or which the shampoo is for use in Make it suitable for toddlers and toddlers, so that it can be called baby shampoo.

The present invention also encompasses aftershave lotions which are in the form of "preshave ¹¹ " or "aftershave lotions". Preshave lotions can come in two types: 1) Those that are mainly intended to soften the beard, usually contain a wetting agent as an active ingredient in a base of alcohol, water and glycerin, they are perfumed and colored. 2) Alcohol solutions for use before the electric shave as a strong astringent that contracts the skin and erects the whiskers. Aftershave lotions are usually similar in composition to astringent lotions, with a higher percentage of alcohol used for cooling

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dor skin serves and prevents irritation. The alcohol also acts as a mild antiseptic against infection.

Aftorshave lotions consist of a solution of perfume in water and alcohol. The alcohol content is between 50 and 70 %, with the perfume content between 0.5 and 1.5% , depending on the amount of alcohol used.

Additional substances are often incorporated such as:

1) Humidifier - up to 3 % glycerine, propylene alcohol

hol or sorbitol solution;

2) Saccharin - to overcome the bitter taste of the

Alcohol denaturant;

3) menthol for cooling and as an anesthetic.

The amount of diol used as an antibacterial agent in the present invention or diol ester is about 0.05 to 5.0 wt% _e ~, preferably about 0.1 to 0.5 wt .-%, based on the weight of the total composition.

The 1,3-diol contains about k to 15, preferably 6 to 10 carbon atoms in the diol chain. Particularly suitable diols for use in the present invention are 1,3-heptanediol, 1,3-octanediol, and 1,3-nonanediol. If a mono- or diester is used, the number of carbon atoms in the diol chain is about k to 15, preferably k to 10. The number of carbon atoms in the ester group can be in the range from about 2 to 15, preferably about 3 "to 10, vary. Particularly suitable diol esters are 1,3-octane

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diol-1-monopropionate and 1,3-butanediol-1-monooctanoate.

The particularly preferred diols according to the invention are 1,3-diols of the following chemical formulas:

R-CH-CH ₂ -CH ₂
t ι

OH OH

in which R is an n-alkyl radical having 6 to 12 carbon atoms. The preferred 1,3-diols must therefore have at least 6 carbon atoms in the chain (R = s3). Diols with fewer carbon atoms are not as effective as antibacterial substances or additives. The preferred diols contain 7 to 9 carbon atoms in the chain (R = 4 to 6).

The preferred monoesters of the present invention have the following chemical formulas:

R-CH-CH ₂ -CH ₂ R-CH-CH ₂ -CH ₂

II Il

OH OCR ₁ OCR ₁ OH

Il Il

0 0

in which R is an n-alkyl chain with 0 to 12 carbon atoms and R-, an n-alkyl chain with 1 to 1? Carbon atoms means. The esters can therefore have 3 to 15 carbon atoms in the diol portion of the molecule. The preferred monoesters contain 4 to 10 carbon atoms in the diol portion

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(R = 1 to 7) of the molecule and 3 to 10 carbon atoms © (R ₁ = 2 to 9) in the ester part of the molecule. Particularly suitable monoesters are 1,3-butanediol-1-monooctanoate and 1,3-octanediol-1-monopropionate. These monoesters can exist in two different forms. Form A is the 1-monoester form. Form B is the 3-monoester form.

Another ester form which is suitable for certain applications is the diester C of the formula

R-GH-CH ₂ -CH ₂

ι ι

OCOR ₁ OCOR ₁

in which R denotes an n-alkyl chain with 0 to 12 carbon atoms and R- denotes an n-alkyl chain with 1 to 17 carbon atoms. The preferred diesters contain about 1 to 8 carbon atoms in the diol portion (R = 1 to 5) and 3 to 3 carbon atoms (R-, = 2 to 9) in the ester portions of the molecule. Although the diesters are generally not as active as the monoesters, they are useful in those cases where their physical properties (eg their increased lipophilic character) are particularly desirable.

Both for the 1,3-diols and for their esters it is essential that the molecules be linear and that the hydroxy and / or carbalkoxy (ester) groups be attached to the first and third Carbon atom are bonded. This 1,3-difunctionality makes these compounds particularly suitable for use in humans and animals because of their inherent safety

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suitable. Other diols suitable for use in the present invention are 1,3-hexanediol, 1,3-decanediol and 1,3-undecanediol.

The diols and diesters of the present invention can be prepared by suitable methods such as the Reformatsky reaction with subsequent reduction or by the Prins reaction of formaldehyde and the appropriate olefin.

Various tests were carried out to illustrate the invention, the results of which are given in the examples below and tables are listed. In Table I are the results of the toxicity measurements for a number of Dihydroxy compounds including the 1,3-diols summarized. These studies were carried out with rats.

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Table I:

Toxicity data for various diols.

link Dihydroxy compound 1 1,3-butanediol 2 1,3-pentanediol 3 1,5-pentanediol k 1,3-hexanediol 5 1,5-hexanediol 6th 2,5 hexanediol 7th 1,6-hexanediol 8th 1,3-heptanediol 9 1,3-octanediol 10 1,3-nonanediol 11 1,3-decanediol 12th 1s3-undecanediol

Oral LD _c

PV

( 7th Days)

29 g / kg

> 20 g / kg

2 g / kg

> 20 g / kg> 20 g / kg

2 g / kg

5 g / kg

> 20 g / kg> 20 g / kg> 20 g / kg> 20 g / kg> 20 g / kg

egg

Single dose in rats;

= lethal dose for 50 # kill.

^ Q are a common measure of a compound's toxicity. The LD ^ values represent the dose at which 50 % of the animals are killed, this dose being tested per unit weight of the animals. The higher the LD ^ Q value, the lower the toxicity. The figures in Table I show that the 1,3-configuration of polyalcohols !! are the least toxic. In the case of compounds with this structural feature, the LD ^ _Q values are much higher. The LD ^ Q values in Table I were obtained by giving the test animals single graded doses of the test compounds orally and observing them for a week. The number of animals killed in each group was noted and the dose required to kill 50% of the animals was recorded as the LD ^ _n value. In many cases no animal was killed, even at a dose of 20 g / kg (about as much as can be given to a rat in one dose), which is the basis of the ">20" values in the table.

The toxicity values for the esters are shown in Table II below. Some common antimicrobial agents are also listed. They are all much more toxic (lower LDc _n -V / erte) than the diols or the esters.

Table Ht Antimicrobial Agent Oral LDc ₀ (rats)

Diolester> 20 g / kg

Hexachlorophene ² (G-II) 0.104 g / kg

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Table II (continued):

Bithionol 6.6 g / kg

Dichlorophene (G-4) ² 1.24 g / kg ⁵

Roccal ^ 0.23 g / kg

o-phenylphenol ^ 0.14 g / kg

LDj-Q = lethal dose for 50 % kill;

ρ
Source: Mfg. Chemist and Aerosol News, July (1969) 5

- ^ guinea pigs;

^ "Handbook of Toxicology, Volume I.

To further explain the present invention and in particular to demonstrate the superiority of the 1,3-Dio » Ie and esters as bacteriostatic agents and mold inhibitors the following microbiological tests were carried out.

Example 1;

Nutrient broth was used as the basic nutrient for the growth of all microorganisms tested. 5 ml of the nutrient broth (Difco Co.) was placed in 18 mm 150 mm test tubes and the base medium was sterilized with steam at 1.05 kg / cm for 15 minutes. After cooling, sufficient amounts of the various compounds were added to the base medium to maintain the concentrations used. Usually a final concentration of 0.2, 1 and 2 % was used.

After the chemicals were mixed with nutrient broth, the tubes with the various test

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Organisms vaccinated. The partial microorganisms were before Has been bred in Nänrorüne for 25 hours, and 1 Drops of the compacted microoial suspension were made added to the tubes.

The tubes with the chemicals and microorganisms were then at the optimal growth temperature, which is specified for each tested microorganism, ihüuoiert. The temperature was either 37 or 30 C. The growth in the tubes and chemicals containing tubes was observed visually. iJacii a suitable incubation period was one in each case small amount (aliquot) of the test solutions on an agar plate deleted to confirm visual readings for the presence of microbial growth Could.

The results are shown in Tables III and IV. The "Minimum Effective Concentration" is the smallest concentration of the additive that the growth effectively prevented under the Vex search conditions.

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O ■ δυο

Table III:

Protective effect against bacteria.

link

1,3-heptanediol 1,3-nonanediol

1,3-octanediol-1-nionopropionate 1,3-butanediol dipropionate

Minimum inhibitory concentration against

P. aeruginosa Salmonella typhimurium E. coli Λ * / 0 0.5% -ι ο /
. \ / Q 0.5 % O 0 0.2 % ο ο /
£. / Q 0 0.2 %

Symbol: O = not tested "

From the tables above it can be seen that the effectiveness of these substances against a broad spectrum of bacteria is proven by the representative values in Table II , 2 % are effective against Salmonella. These experiments were carried out under conditions conducive to vigorous growth of the organisms. Under the conditions of normal use, the test compounds are also effective in lower doses. Salmonella organisms play an important role in public health. All organisms of this species are considered to be pathogens for humans.

The additives according to the invention are also effective for # Inhibition of molds as shown in Table IV below.

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Table IV:

Protective effect; against mold. Effective minimum concentration against

Trichoderma Botrytis P. roquefortii Fusarium

Pre-binding 12688 * 9435- * 6988 * - 10911 * ^B ' ^{fulv a A} * ^{nise r A} ' ^flavus

1,3-pentanedioi + + 2 % +++ +

1,3-heptanediol 1% 1% 0.2% 1% 0.2% 0.2% 1%

1,3-pentanediol 0 0 1% 0 0 1% 0

ω monopropionate

2 1,3-octanediol 0.2% 0.2 ^ 0.2% 0.2% 0.2% 0.2% 0.2% ao monopropionate

J 1,3-butanediol 0.2% 0.2% 0.2 % 1% 0.2% 0.2% 0.2% ^, dipropionate

2 1,3-butanediol »0 0 0 ₅ 2% 0 0 0.2% 0 ^ monooctanoate

⁰⁸ 1,3-pentanediol 0 0 1% 0 0 0.2% 0

monooctanoate

Symbols: + = no effect at 2% _e. The smallest amount tested in this experiment was 0.2% _e

0 = not tested

* All reference numbers for the microorganisms are the same according to the American Type Culture Collection '

Claims (5)

Claims; 1. soap, shampoo and Rasierwassorzusammen reduction of high quality with bacteriostatic properties, characterized daaurch that it comprises about 0.05 to 5.0 wt -.% Of an aliphatic diol or its üster containing said diol odor of these diol esters about 4 contains up to 15 carbon atoms in the aliphatic molar chain and the hydroxyl group or the ester group is bonded to the first and third carbon atoms. 2. Composition according to claim 1, characterized in that that the diol ester is a monoester containing about 2 to 15 carbon atoms in the ester group. 3 «Composition according to Claim 1, characterized in that it contains 0.1 to 0.5% by weight of diol or diol ester contains. 4. Soap composition according to claim 1, characterized in that sic contains a sodium salt of a fatty acid having 10 to ZZ carbon atoms. 5. Composition according to claim 4, characterized in that that they as Üiol 1,3-octanediol, 1,3-heptanediol or 1,3-nonanediol. 309842/1048 6. Composition according to claim 4, characterized in that that they are 1,3-butanediol-1-monooctanoate as a diol ester or 1,3-octane-1-monopropionate contains. For: Esso Research and Engineering Company Dr, H. J. Wolff attorney Re c 309842/1048