DE10007198A1 - Use of addition product-forming unsaturated acids, esters, salts, aldehydes or ketones in a wide variety of deodorant compositions such as antiperspirants, whole body deodorants or mouthwashes - Google Patents

Abstract

Use of alpha ,beta -unsaturated esters, alpha ,beta -unsaturated carboxylic acids (or their anhydrides or salts) or alpha ,beta -unsaturated aldehydes or ketones (especially of the terpene series) as deodorants, on account of their capacity for forming addition products with dangerous and troublesome volatile (especially S- and N-containing) materials.

Description

A.) State of the art

In rotting processes, both aerobic and especially anaerobic wake you up send microorganisms (bacteria, fungi) organic substances broken down so that as a substance Interchangeable volatile sulfur and nitrogen compounds such. B. sulfur hydrogen, low mercaptans, ammonia or methylamine are formed. These substances are not only harmful to health, but also annoying to disgusting.

The problem affects many areas of private and public life. For example The animal husbandry that is common today in the home (pets) often leads to strong odors made from litter boxes or hamster, rabbit or sea filled with litter pig cages. Camping toilets are also an odor problem collection of compostable waste introduced to municipalities and for waste a similar smell problem. Solutions to these problem areas, which Interfering with the place of odor generation are proposed in DE 198 37 539.

Another area in which smells can be extremely disruptive is man himself. His body surface is both on the outside of the skin and inside colonized on the mucous membranes of the digestive tract by microorganisms. These are only partially desired and feed on the food of their host or its substance exchange products such as B. sweat or faeces. Your own metabolic products are Frequently volatile sulfur and nitrogen compounds, which the unpleasant body Generate the smell of a lot of people, especially in the case of over- or under-functioning of individual people Bodily processes.

The problem areas of human hygiene are presented in detail below will.

One of the most noticeable odor problems is certainly caused by the decomposition of humans sweat. Only fresh sweat is odorless. However, the skin is through Bacteria, in particular, of the Pseudomonadaceae family, which are found in sweat cleave contained oligopeptides and, like existing amino acids, oxidatively deaminate to lower carboxylic acids and decarboxylate to amines. Out  sulfur-containing amino acids such as cystine and cysteine are also thiols (mercaptans) released. In addition, fats are broken down into fatty acids. The Ge is particularly strong The formation of odors naturally occurs on the more perspiring areas of the skin, i.e. in the Ach selenium and genital area, but also on the feet and possibly on the hands. Hairiness, Clothing or skin folds (occlusion conditions) increase the problem.

The odor intensity can be checked by washing with water and soap or soap-like Products. As this is necessary, depending on the intensity of the sweating, several times a day are particularly interesting for long-term methods that work outside the company. To There are four methods of reducing odor generation.

The most radical is surely the reduction of sweat secretion by antiperspirant acting substances. Most common nowadays are aluminum salts, e.g. B. Alumi nium chloride hexahydrate, aluminum chlorohydrate or aluminum zirconium hydroxochloride Hydrates. However, there is growing concern against the use of these substances hold. Not only should one not reduce the production of sweat unnecessarily, unless it is has increased pathologically. Rather, the aluminum salts are particularly effective on those who are more sensitive Skin extremely irritating because of its dehydrating effect cell damage can cause. They often lead to allergies, including a cross allergy to nickel are suspected of triggering or causing Alzheimer's disease accelerate and are also ecotoxicologically questionable. Damage aluminum salts the fine root network of plants by disrupting cell division. Because all cosmetics ultimately washed off, they inevitably end up in the wastewater and thus in the Environment.

The second method is to inhibit the odor-emitting bacteria or kill. As a result, the balance of natural settlement becomes uneven brought important and possibly even destroyed the skin flora. Because there is still no selective Remedies only for the odor emitters, apart from the fact that they are also partially useful represent linge. As active ingredients such. B. triclosan, bronopol, hexachlorophene, chlorine hexidine and other quaternary ammonium compounds as well as amphoteric surfactants in question, as well as some of the aluminum salts mentioned above, in addition to the astringent also have an antibacterial effect. Except for the latter, the aforementioned effects fabrics are only used in special areas. As mild and the bacteria only hem Means such as farnesol and various glyceryl esters of long-chain Carboxylic acids used. However, their effects are not always fully satisfied judged in place. Ethanol can also be used without the addition of Remanent active ingredients and in a low concentration only a short-term disinfection works. But a certain potential for irritation is also attributed to alcohol.

The third method consists of masking the smell, as it has for centuries practiced with more or less success. With fragrances you try the un wanted to overlay body odor. One consequence of these considerations was that Creation of so-called perfume deodorants. However, the fragrance composition through the Verbin with the undesirable body odors often a large deviation in experience an uncomfortable direction or the masking is not completely successful. In addition It is also not for everyone to scent yourself so strongly or to smell yourself let the deodorant dictate.

The fourth method is the removal of odor. This path has also been taken in the past. There were attempts made with ion exchangers that chemically bind or cure odorous substances should sorb. There has also been reports of an "odor extinguisher" based on zinc ricinoleate, which should form an inclusion compound with the odor-forming substances. Around however, these substances have become quiet. Chlorophyll, too, has been very busy for a while beloved odor-binding agent, but is not least due to technical difficulties gone out of fashion.

Since this procedure does not damage the skin or the natural skin flora if a strong fragrance has to be accepted, there is a need for reliable odor-removing substances which are not harmful to the skin and which change the composition of the human skin flora as little as possible.

Another problem area of human hygiene is bad breath.

It arises partly in the oral cavity itself. Staphylococcus bacteria, Enterococcus and Streptococcus, for example, live on teeth and gums (tooth coating, plaque) and feed on food residues whose decomposition is similar to that of the Sweat in addition to the main product lactic acid to other lower carboxylic acids, Mercaptans, amines and ammonia can result. The most common cause is periodontal disease tis.

Bacterial growth can be stopped using a variety of methods. Regular cleaning and cleaning of the interdental space already eliminates the problem in the early stages. Removal of tartar and treatment of tooth decay and periodontitis help in the advanced stage. Nevertheless, many people are bothered by mouth smell.  

Bad breath can also be an expression of a stomach problem. Under one load Settlement of the stomach with Helicobacter pylori suffers from a large number of people. One of the The metabolic products of this germ is ammonia, which goes through the esophagus into the mouth the host's cave is excreted. The excretion products of many anaerobes like Enterobacteriaceae, which often colonize the stomach and intestines of humans, In addition to the odorless methane, unpleasant smelling gases are also the way find the top of the digestive tract. From the moist environment of the oral cavity the odorants are then gradually released.

Mouthwashes and gargle preparations in particular, but also toothpastes, are becoming over covering the bad breath with flavors, mostly peppermint, spearmint, Menthol, anise, eucalyptus, clove and wintergreen oil. However, as with the Des odorants described, the masking is not always complete. In addition, these are Ge flavors are not entirely popular and on top of that there is an intense smell especially after menthol and mint flavors, mostly as an indicator of the underlying pro blem.

Here, too, there is a need for reliably odor-removing, non-toxic and substances not irritating to the oral mucosa, which are also due to the tons Consumption of such products must not be harmful to the environment. You should have no problem in Toothpastes, mouthwashes and gargle water can be incorporated and at the same time inexpensive be enough to enable wide use.

It can also become uncontrollable at the other end of the human digestive tract ren decomposition gases come out, namely in the case of an artificial intestine ganges (anus praeter). Here, the intestinal exit had to be relocated and will not more closed by a consciously controllable muscle, the anus, but ent involuntarily empties the contents of the intestine into a connected bag. The human gut also produces about two to three liters of gases a day, the capacity of one at the body with a portable and invisible container. Hence the bag have a gas-permeable outlet. The gases used to remove the rie passed through a filter. Known means of odor removal are physically working absorbents such as bentonites, activated carbon, cellulose and moles molecular sieves (zeolites). However, the mode of action of these substances is not entirely satisfactory lend how many patients with anus praeter is shamefully aware. The use of fabrics in it would be desirable to have filters that permanently trap the odorous substances. Also one Place in the pouch itself for the immediate removal of smelling substances from the decomposition  the faeces would be of interest. At the same time, the fabrics should be reasonably priced be to enable permanent use.

B.) Description of the invention

As described in detail in DE 198 37 539.5, some vinylogous carbonylver meet bonds. (Electron acceptor compounds) the required property profile in all Score and are therefore ideal as an odor trap.

The task could therefore be solved in that the vinylogous compound α, β-unsaturated ester or an α, β-unsaturated carboxylic acid. Esters are in themselves at the end of the reactivity series and acids are generally considered to be no longer active enough. However, acrylic acid and its esters substituted with electron-withdrawing groups show how enough activity.

Are these additional substituents again carbonyl groups or carbonylanalo ge, it is practically double vinylogous carbonyl compounds. The fiction Compounds according to the invention are therefore in particular unsaturated biscarboxylic acids such as Fu Martic acid (E-2-butene-1,4-diacid) and maleic acid (Z-2-butene-1,4-diacid) as well as their Esters according to formula I. Their salts also show activity, but this is not always so high. The compounds of the invention are also polyunsaturated unsaturated Monocarboxylic acids such as sorbic acid (E, E-2,4-hexadienoic acid) and their esters and sal ze according to formula II. Here too, nucleophiles attack because of the vinylogy principle terminal double bond (C4 = C5). This receives its special reactivity through the electron-withdrawing effect (-I and -M effect at the same time) of the neighboring ones, through which Carboxyl group additionally substituted electronically substituted double bond (C2 = C3) and through the mesomeric stabilization of those introduced by the nucleophilic attack Charge by delocalization over 6 atoms.

The substances mentioned are not very dangerous. The fumaric acid comes for example in the Citric acid cycle, the elementary aerobic energy production mechanism of Cells. Sorbic acid is found in numerous fruits, e.g. B. in cranberries or Vo yellowers. These acids can only be classified as irritating in a very concentrated form. Also The water hazard class is only 1, so that there are no sewage problems fear.

There are no restrictions on the alcohol component of the esters, certainly should Long chain residues can be avoided as they increase molecular weight lower the percentage by weight of the actually active double bonds and Have an influence on water solubility. Are particularly preferred due to their toxicolo properties of the mono- and diethyl esters of fumaric and maleic acids and Sor ethyl binsate.

Also higher carboxylic acid, that is to say on the double bond (s) alkyl- or aryl-substituted carboxylic acid Ren can be considered, but the reactivity decreases and other pathways also be hit. For example, cinnamic acid (3-phenyl 2-propenoic acid) and its esters to a further mechanism of odor control, namely an odor depression caused by electron-donating substituents like Me Thoxy groups in the ring is not affected and the double bond in the α, β position Carboxyl group is not required (DE 198 04 042).

Fumaric and maleic acids are extremely inexpensive. Maleic acid is obtained from Er heat malic acid or by oxidation of benzene or butenes to maleic acid drid followed by water addition. It is more water soluble and more acidic than fumaric acid. These occurs in numerous natural substances, e.g. B. in tobacco, arnica, senecio, corydalis, fumaria officinalis (earth smoke), heather and Icelandic moss, in truffles, morels, chanterelles and toadstools. It can be enzymatically converted by fungi such as Rhizopus Produce nigricans or Aspergillus fumaricus from glucose and starch or by catalyti win cal or UV-induced rearrangement from maleic acid. Fumar like maleic acid are approved for use in food, pharmaceuticals and cosmetics. Sorbic acid obtained from Sorbus aucuparia (rowan berry) or synthetically by implementing Crotonaldehyde with ketene followed by acid hydrolysis and dehydration. It is one approved in food and cosmetics.

Like many fruit acids, fumaric acid is said to have a slightly antimicrobial effect, while sorbic acid inhibits fungi and yeasts in the acidic pH range.

Formula I: RO- (O =) CR ² C = CR ³ -C (= O) -OR ¹

R, R ¹ = H, M ⁺ (e.g. Na ⁺ , ½ Ca ²⁺ ), alkyl- (e.g. methyl-, ethyl-); R ² , R ³ = H, alkyl, aryl z. E.g .: fumaric acid: R, R ¹ , R ² , R ³ = H (E-form), maleic acid: R, R ¹ , R ² , R ³ = H (Z-form)

Formula II: R ⁵ R ⁴ C = CR ³ -R ² C = CR ¹ -C (= O) -OR

R = H, M ⁺ (e.g. Na ⁺ , ½ Ca ²⁺ ), alkyl (e.g. methyl, ethyl); R ¹ , R ² , R ³ R ⁴ , R ⁵ = H, alkyl, aryl, e.g. B.: Sorbic acid: R, R ¹ , R ² , R ³ R ⁴ , R ⁵ = H (E, E-form), The object could also be achieved in that the vinylogous compound is an α, β-unsaturated aldehyde, e.g. B. from the terpene series. The aldehyde group is the most active substitute on the vinylogenic double bond, but an alkyl- or aryl-substituted double bond has lower reactivity than that of the lowest representative acrolein. These compounds have long been known as natural substances. Geranial (E-3,7-dimethyl-2,6-octadienal) and neral (Z-3,7-dimethyl-2,6-octadienal) and citral, a natural mixture, are particularly suitable. Citral is readily available, relatively stable, and its smell is very acceptable due to its fragrance properties. It occurs in numerous essential oils and can be obtained as so-called lemon oil from citrus fruits and as le mongras oil from Cymbopogon flexuosus and C. citratus as well as from Litsea cubeba or by oxidation of geraniol (from geranium and rose oil). The oils and the isolated citral are used extensively in liqueurs, perfumes, cosmetics and cleaning products. The price is extremely low. As with many fragrances, its only health hazard is possible sensitization in humans.

Other less dangerous α, β-unsaturated aldehydes and ketones such as e.g. B. the ionone (2-substituted ethenyl methyl ketones), carvone or verbenone are not cheap and in larger quantities available. For many of the aromatically substituted aldehydes and ketones, e.g. B. cinnamaldehyde (3-phenyl-2-propenal), the above applies to the α, β-unsaturated carbon acids said. In addition, these compounds are due to the aromatic ring practically insoluble in water, also sensitive to light or oxidation, sensitizing and / or are expensive, such as benzalacetone (4-phenyl-3-buten-2-one).

Terpenes, especially citral, can also have weak antimicrobial effects.

Formula III: R ³ R ² C = CR ¹ -CR (= O)

R, R ¹ , R ² , R ³ = H, alkyl, aryl z. B. Geranial: R, R ¹ = H, R ² = Me, R ³ = CH ₂ -CH ₂ -CH = CMe ₂ (E-form), Neral: ditto (Z-form) Benzalacetone: R = Me, R ¹ , R ² = H, R ³ = C ₆ H ₅ , cinnamaldehyde: R, R ¹ , R ² = H, R ³ = C ₆ H ₅ .

Possible applications of the invention will be discussed below:
In any case, only substances that are approved or permissible under the Cosmetics Ordinance are suitable for use in accordance with the invention. However, the latter is a lengthy and expensive process. Therefore, substances that have already been approved will certainly be preferred. Of the substances that are suitable in principle, as outlined above, fumaric acid, maleic acid, sorbic acid and citral have already been approved for use in cosmetics and food. IFRA-approved α, β-unsaturated aldehydes and ketones can also be used as fragrances in cosmetics, sometimes with due regard to the application limits. The same applies to flavors with an FRG Aroma Chemical or FDA approval.

The main benefit of the products according to the invention is that they have an unpleasant smell remove without bringing a smell that the user z. B. a De os a self-determined perfume difficult with a fine fragrance or as with a mouthwash indicates the use of an odor-treating product.

For this reason, fumaric and maleic acid should be preferred. Also sorbic acid is odorless, but it is in the acidic pH range, as it is the case with most cosmetics Is sought, also anti-fungal and bacterial, so that their use in the agents according to the invention for removing odors on the skin and in the oral cavity The effectiveness limit as a preservative must never exceed. Such a way At the same time, the agents themselves are protected against microbial attack.

If additional deodorization by fragrances or aromas is desired, then Of course, they are advantageously selected from the group of α, β-unsaturated aldehydes and ketones be selected and thus bring an additional benefit.

The formulations can be the agents according to the invention as a basis or as an additive substances contained in recipes known per se.

The agents according to the invention are therefore suitable as a basis or additive in armpit, Foot and body deodorants in liquid, gel-like, solid and powdery form. Be These are preferably formulations without long-term disinfectant or antiperspirant effects fabrics. However, the agents according to the invention can also contain disinfectant formulations or antiperspirant mode of action can be added, reducing the proportion of active ingredients can be lowered. The deodorants can be applied in any manner known per se be decorated, e.g. B. as an aerosol, powder, stick, cream or pump sprayer. Except the agents according to the invention are suitable as additives for washing preparations such as Shower lotions, washing syndromes, shampoos or bath products to remove the odor Support cleaning by water.

The agents according to the invention are also suitable as a basis in mouthwashes, teeth pastes or gargling or as an addition to recipes known per se.  

The bags for patients with an artificial colon exit contain a gas outlet system, the ver through a filter to remove the smelling components in the intestinal gases is closed. The gases can advantageously by a filter system that the invention ß means containing liquid. Alternatively, the invention Agents on physically working absorbents such as bentonites, activated carbon, cellulose and Molecular sieves (zeolites) are applied, so that due to the immensely large upper a solid phase reaction is possible. The agents according to the invention also come here preferably maleic, fumaric or sorbic acid because of its low intrinsic odor Question. Also as a template in the loot itself is a solution of the agent according to the invention or formulations from it possible.

The invention is to be explained in more detail below on the basis of exemplary formulations will. The selection is not exhaustive

Mixture for use as armpit deodorant

Ethoxylated, hydrogenated castor oil (40 EO) 1.5% Ethanol, 96% 39.2% Farnesol 0.3% Pentylene glycol 0.3% Fumaric acid 0.5% Sodium hydroxide solution, 10% to adjust to pH 5.5 water ad 100%

Mixture for use as a mouthwash concentrate

Ethanol 72.0% α-bisabolol (85%) 1.0% Sorbic acid 0.6% Calcium fumarate 3.5% Fumaric acid 1.5% Glycerin 1.0% sweetener 0.2% Aroma 2.0% Ethoxylated, hydrogenated castor oil (40 EO) 6.0% Water, purified ad 100%%

Adjust to pH 5 to 6 with fumaric acid / calcium fumarate.

Mixture for use as a toothpaste

Carboxymethyl cellulose 1.5% Glycerin 30.3% Sodium lauryl sulfate 1.0% Dicalcium phosphate 30.0% 1,2-propylene glycol 36.3% Fumaric acid 0.4% Preservative 0.3% Saccharin 0.1% Aroma 0.1%

Mixture for use as a filter material for chair bags (for anus praeter)

Maleic acid 70.0% water 30.0%

Let it soak on zeolites, dry at 40 ° C after saturation.

Claims (7)

1. The use of α, β-unsaturated esters, α, β-unsaturated carboxylic acids, their anhy dride and salts as well as α, β-unsaturated aldehydes and ketones, e.g. B. from the Terpenrei hey, whose capacity to add dangerous and 1 or annoying volatile, especially sulfur and nitrogenous Fabrics lie as a means of removing odors. 2. The use according to claim 1, in particular the use of fumaric acid, Maleic acid and sorbic acid, their salts and esters, primarily the methyl and Ethyl esters, and maleic anhydride, very particularly preferably the use of Fumaric, maleic and sorbic acid; as well as the use of Citral, Geranial and Neral and extracts and distillates containing them, such as lemon, lemongrass or gerani oil. 3. The use according to claim 1. and 2. as a mixture in different ratios nissen, depending on the application, from 1: 100 to 100: 1, preferably 1:10 to 10: 1. 4. The use according to claim 1 to 3 for use in body deodorants of all Kind of like armpit, foot or whole body deodorants as well as washing, showering and bathing de additions, for use in mouthwashes, toothpastes and gargles and for use in filters for or as a template in chair bags for use with anus praeter. 5. The use according to claim 1 to 4 as an aqueous, alcoholic or glycolic Solution with 0.05 to 20 wt.%, Particularly preferably 0.1 to 5 wt.% Of the above α, β-unsaturated compounds or as given by the user to the concentration ions to be diluted concentrates with up to 100% active ingredient. 6. The use according to claim 1 to 5, mixed with auxiliaries such as. B. Tensi den, emulsifiers, other solvents, terpenes, terpenoid solvents, care substances, oils and waxes, complexing agents, pH regulators, consistency regulators, sequestering agents, adjusting agents, blowing agents, dyes, fragrances and Flavors for varying the olfactory properties etc. These are preferred Non-hazardous and easily biodegradable. 7. The use according to claim 1 to 6 as an additive to known body des odorants of all kinds in addition to disinfectants, antiperspirants and / or cleaning effect to reduce or prevent odors.