CA1076475A

CA1076475A - Smell-removing agent

Info

Publication number: CA1076475A
Application number: CA266,737A
Authority: CA
Inventors: Rudolf Kurner
Original assignee: Individual
Current assignee: Individual
Priority date: 1975-12-19
Filing date: 1976-11-29
Publication date: 1980-04-29
Also published as: ZA766967B; JPS5279029A; SE436968B; SE7612860L; CH622700A5; NL7613664A; DE2557365C2; IT1064474B; GB1571517A; ATA868176A; JPS5722589B2; FR2335260A1; DE2557365A1; FR2335260B1; BE849182A

Abstract

ABSTRACT OF THE DISCLOSURE
The use of polyvinyl pyrrolidone in deodorizing compositions.

Description

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The present invention relates to a method of deoderizing a substrate and a composition for use in said method.
Heretofore offensive odours have been modiied or covered by addition of pleasantly smelling substances. This applies to technical fields as well as to cosmetics and hygienics. Thus, a diluting and covering effect, respectively, was achieved.

, Another possibility of covering unpleasant odours lies ;
in the use of film~forming materials, such as zinc ricinoleate or copolymers of polyvinyl pyrrolidone and vinyl acetate, which apparently fix the odour molecules by encasing fine suspended particles. However, when film-forming materials are added to scented smell-covering agents, the substrates are prevented from releasing scent molecules since they are coated with non-evapora-ting films. Even desirable odours are, thus, suppressed or dampened. This so-called "cheese-plate cover" effect makes it impossible to use such compositions for arm-pits, feet and the like since it is generally known that the plugging of sweat pores may result in serious irritations of the skin. Furthermore, the 20 stickiness of thase compositions is unfavourable in a physiolo-gical sense.
Antiseptic agents are used to prevent bacterial decomposition of sweat and the development of body odours in the arm-pits, on feet and the like. In this way, disagreeable odours are stopped before they may start.

r' ' Only lauryl methacrylate is considered a true smell-destroying compound. It acts by generating less odorous copoly-mers. A chemical effect is utilized to destroy odours. The chemical nature of the compound and the fact that it is normally manufactured as 80 ~ concentrate in hydrocarbons does, however, ` not permit its use on humans.
All previous attempts to explain the mechanism and '~ ' .... .

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effects of so-called "smell-destroyers" have involved tests in the gaseous phase in order to simulate the phenomena accompanying the perception of smells as closely as possible. Former tests (see H.P. Fiedler, "Der Schweisse", Editic Cantor, Aulendorf, 18.
Beiheft der Arzneimittelforschung, 1968, page 494) have shown, for instance, that essential oils and active substances in smell-destroying compositions primarily occupy the olfactory cells of the human nose leaving no room for "stink molecules". All known smell-destroying agents have the disadvantage of showing no selectivities for offensive odours.
German patent No. 899 248 describes the use of polyvinyl pyrrolidone in preparing so-called dry perfumes. The perfume oil may be added in "dry form" to powdery compositions such as bath-salts. It is completely soluble in the bathing-water and releases its scent freely. Compositions of this nature release fragrant substances to the surroundings, will however, not remove odours.
It has now been found that polyvinyl pyrrolidone soluble in water and alcohol acts as true smell-removing agent. The term "soluble in alcohol" means that the compound can be dissolved in lower aliphatic alcohols having up to 3 carbon atoms.
According to the present invention therefore there is -provided a method of deoderizing a substrate which comprises applying théreto a deoderizing composition the improvement in ~ ;
which the deoderizing composition includes polyvinyl pyrrolidone.
The present invention also provides a compound for use in deoderizing a substrate comprising a solution or mixture of polyvinyl pyrrolidone.
The polyvinyl pyrrolidones soluble in water and alcohol suitably have a k-value of about 5 to 150, preferably about 10 to 95 and more preferably of about 13 to 35. The k-value may be defined by the following equation:

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log n rel C
in which ~ rel is the viscosity of the solution relative to the solvent and c is the concentration in grams per 100 milliliters of solution. The above mentioned polyvinyl pyrrolidones generally have an average molecular weight of about 5000 to 2,000,000.
Preferred are compounds having an average molecular weight of about lO,000 to 1,000,000 and especially of about 13,000 to 450,000.
The polymeric polyvinyl pyrrolidone, soluble in water and alcohol, is suitably employed in solution or admixed with conventional pharmaceutical, cosmetic or technical carriers or synthetic materials.
Suitable solvents are water and mono-- or polyhydric alcohols having up to 6 carbon atoms, preferably water and/or mono- or polyhydric aliphatic alcohols having 1 to 3 carbon atoms. If desired, di- to hexahydric alcohols having up to 6 carbon atoms may be added in amounts up to 50 % by weight, pre-ferably up to 30 % by weight and especially up to 10 % by weight.

The solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec. butanol, amyl alcohol, 2-ethyl-1-hexanol, cyclohexanol, phenol (50C), ethylene glycol, propylene glycol, 1,3-butane diol, 1,4-butane diol and glycerol; ketone alcohols such as diacetone alcohol; aliphatic carboxylic acids such as formic acid, acetic acid and propionic acid; ether-alcohols such as "Solvofen" (a trade mark) glycol ether, ; diethylene glycol, triethylene glycol, hexamethylene glycol, polyethylene glycol 400 and 2,2-thio diethanol; lactones such as butyrolactone; esters such as ethyl acetate; ketones such as 3Q methyl cyclohexanone; chlorinated hydrocarbons such as methylene dichloride, chloroform, ethylene dichIoride; dichloro monofluoro methane and chloro difluoro methane; lactams such as 2-pyrrolidone, ~07~75 N-methyl-2-pyrrolidone and N-Vinyl-2-pyrrolidone; amines such as butyl amine, cyclohexyl amine, aniline, ethylene diamine, pyridine, morpholine, 2-amino ethanol, diethanolamine, tri-ethanolamine, aminoethylethanol amine, 2-hydroxyethyl morpholine, and 2-amino-2-methyl-1-propanol; and nitro paraffins such as nitromethane, and nitroethane. Together with lower aliphatic alcohols having 1 -to 4 carbon atoms and preferably 2 to 3 carbon atoms, the following hydrocarbon halides may be used: trichloro fluoro methane, dichloro difluoro methane, 1,1,2-trichloro-1,2,2-trifluoro ethane, 1,2-dichloro-1,1,2,2-tetrafluoro ethane and l-chloro-l,l-difluoro ethane. 'rhe mixing ratio of hydrocarbon to alcohol generally lies between 90/10 and 60/40 parts by weight, preferably between 80/20 and 70/30 parts by weight. The concen-.
tration of polyvinyl pyrrolidone in the solution is at least - about 0.1 % by weight, preferably 0.2 to 10 % by weight and especially to 0.3 to 3.0 % by weight, based upon the total weight of the solution.
` Suitable carriers are water-soluble, water-insoluble and water-swellable carriers. Water-soluble carriers include~
water-soluble sugars such as dextrose, lactose, levulose and i.-~
cane and beet sugar, sugar alcohols such as sorbitol; inorganic or organic salts such as aluminum potassium sulfate, aluminum sulfate, ammonium chloride, ammonium sulfate, barium chloride, calcium chloride, chromium sulfate, copper sulfate, iron sulfate, magnesium chloride, mercury acetate, nickel nitrate, lead acetate, potassium chloride, potassium sulfate, potassium dichromate, sodium bicarbonate, sodium chloride, sodium nitrate, primary sodium phosphate, sodium pyrophosphate, sodium sulfate, sodium sulfite, sodium thiosulfate, silver nitrate, and zinc sulfate;
lower water-soluble polyethylene glycols such as polyethylene glycols having a molecular weight up to about 600.
Water-insoluble carriers include vegetable and animal ~7~ S
oils such as olive oil, palm oil, fish oil, train oil; animal and vegetable fats such as coconut oil, lard, tallow and spermaceti; mineral oils and mineral oil products such as paraf-fin oil, petroleum, vaseline and stearin; inorganic carriers such as diatomaceous earth, aerosil, talcum, asbestos, rock wool and silk; and organic insoluble carriers such as wood flour, cellu-lose, wood pulp, and textile fibers.
Water-swellable carriers include plant rubbers such as gum arabic, tragant, alginates and karaya;~and natural or synthetic resins such as shellac, ethyl cellulose, methyl cellu-lose, carboxymethyl cellulose, and dextrines. ~ -When mi~ing polyvinyl pyrrolidone with carriers, the weight ratio suitably lies between about 0.1/99.9 and 99/1.
Preferred is a weight ratio of polyvinyl pyrrolidone to carrier of about 10/90 to 90/10 and more preferably of about 25/75 to 75/25. In spray compositions, the smell-removing polyvinyl pyrrolidone is generally used in amounts of 0.3 to 5 ~ by weight, preferably 0.5 to 3 % by weight and especially 1 to 2 % by weight of the total spray composition without propellant.
In lotions, the polyvinyl pyrrolidone is usually employed in amounts of 0.1 to 5 % by weight, preferably 0.5 to 3 % by weight and especially 1 to 2 % by weight of the total lotion.
In tablets, the polyvinyl pyrrolidone is usually employed in amounts of 0.1 to 99.9 % by weight, preferably 10 to 99.0 % by weight and especially 40 to 98 % by weight of the tablet.
The smell-removing agent may be used in combination with typical smell-improving additives for technical, cosmetic, medical and hygienic fields. Examples for these known additives are taste-improving agents, flavours, perfumes, fixatives, anti-oxidants, preservatives, dyes, solvents and/or dispersion bases , ~ :

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such as creams or lotions. Th~ mentioned materials are employed in usual concentrations.
When using the smell-removing agent in deoderizing compositions, the concentration of the aqueous and/or alcoholic solution of polyvinyl pyrrolidone or of the mixture of polyvinyl pyrrolidone with carriers normally amounts to about 5 to 100 %
by weight, preferably 10 to 100 % by weight and more preferably 20 to 100 % by weight of the total composition.
The use of polyvinyl pyrrolidone in the above mentioned concentrations results in smell-removing compositions which completely remove bad odours for long periods, i.e. for 24 hours or longer. Polyvinyl pyrrolidone is especially suited for removing odours considered upleasant, repulsive, nauseous or otherwise offensive by humans and animals.
Polyvinyl pyrrolidone used as sole active substance in alcoholic or aqueous solutions (as deodorant spray for arm-pits, feet etc.) guarantees complete freedom of body odours for an -~
entire day. Should a smell of sweat have already developed, it will be spontaneously removed when sprayed once with the solution.
If an aqueous solution of polyvinyl pyrrolidone in any concentra tion is then used for washing, followed by rinsing with clear water, the typical smell will disappear completely and will not return. The same spraying solution also removes the smell of onions or pickled herrings from hands. Even the smell of rotting flowers or decaying meat, of feces, or offensive odours from garbage cans as well as undesirable kitchen odours may be removed.
The same applies to tobacco smoke, cadaverous smells, bad breath especially that caused by suppurating wounds in the mouth, and strong-smelling cheese.
When using polyvinyl pyrrolidone as smell-removing agent, the composition may also contain perfume oils which will fully release their individual scent without being impeded by the . . ~ ': ' 1 . ' ! . . . ,. , .~ , ', ', ' . . .

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active compound. The addition of cosmetic oils for skin-care is also possible and will not interfere with the smell-removing effect of the composition.
The following examples are illustrative of the present invention. Unless otherwise stated, all parts are parts by weight.
Example 1 A deodorant spray is prepared by dissolving 1.0 parts of polyvinyl pyrrolidone and 0.5 parts of perfume oil in 28.5 parts of alcohol. The solution containing the active substance is then used to fill containers in a conventional way while adding 35.0 parts of Frigen 11 ( a trade mark) and 35.0 parts of Frigen 12 ( a trade mark) as propellant.
Example 2 A deodorant spray is prepared by dissolving 0.5 parts of polyvinyl pyrrolidone, 1.5 parts of isopropyl myristate and 0.5 parts of perfume oil in 28.5 parts of ethanol. The solution containing the active substance in then filled into containers by conventional means, adding 70.0 parts of Frigen 12/114 - 40/60 ( a trade mark) as propellant.
Example 3 An aqueous lotion (room spray) for mechanical spraying devices is prepared from 10.0 parts of polyvinyL pyrrolidone, 89.8 parts of water and 0.2 parts of potassium sorbate.
Example ~
A deodorizing mouth-rinse is prepared from 1.0 parts of polyvinyl pyrrolidone, 98.7 parts of distilled water, 0.2 parts of potassium sorbate as preservative and 0.1 parts of saccharine.
Example 5 The hands of several test-persons were contacted with freshIy cut onion pieces. After rinsing with water, the hands - still had a specific and rather penetrating smell. Even repeated washing with water and soap could not remove this smell which 1~7~75 seemed to be fixed in a chemosorptive way to the keratin of the skin.
When the hands were washed once with an aqueous 1 %
solution of polyvinyl pyrrolidone and rinsed with clear water, the typical smell disappeared completely and did not return.
Example 6 A solution of polyvinyl pyrrolidone in water (3 % by weight) was applied to the arm pits of several test persons.
Body odour already present was removed completely and did not return for 24 hours. The protection against body odour given by the solution lasted about 14 hours longer than with commercial compositions on the basis of antiseptic substances.
Example 7 .~.
Commercial polyvinyl pyrrolidone powder was diluted to the use-concentration by stirring 2 grams of the compound into 98 grams of water.
Example 8 The solution of Example 7 was employed in the following tests:
(a) Filleted fish was placed into the solution for a short time, i.e. less than 1 minute. After removal of the fillets from the solution, the typical fish odour had disappeared completely.
(b) An offensively smelling dish rag was immersed into the solution and squeezed several times to ensure thorough wetting.
This took no more than 1 minute. After removal, the dish rag was ~ completely odourless.
- (c) Rotting stems of, for instance, orchids and poppies which develop an especially repulsive and penetrating smell, were dipped into the solution for a short time, and the vases were ~ ;
also cleaned with the solution. After this treatment, the offen-si~e smell had disappeared.

(d) Meat, the surface of which showed some decay was placed ' ' ' ' ~ :

~L07~i~75 into the solution ~or about 2 minutes and then rinsed with clear water. The mould which had already appeared as well as the black discoloration of the surface and the nauseous odour were completely gone. The meat was again edible.
(e) A sausage which had been stored for 14 days showed mould at the cut surface and its skin was greasy. After having been placed into the solution for 2 minutes, the mentioned superficial traces of decay had disappeared, and the sausage could be eaten.
(f) Natural skin for sausages had a bad odour and was greasy. It was placed into the solution where the mentioned defects disappeared completely. The hands of the person con-ducting this test had also become odourless.
(g) Hands which had been in contact with pickled herrings were washed in vain several times with water and soap. After immersing the hands into the solution and drying them, no smell could be detected, and the smell did not return.
(h) Within a period of 6 months, fifty persons of both sexes and of different ages were cured by an especially repulsive type of bad breath. This odour known as "foetor ex ore" is caused by gingivitis, stomatitis ulcerosa, dentitio difficile, infected tooth extraction wounds and the like. The test-persons rinsed their mouths vigorously with the above solution. The odour was removed spontaneously and completely. No undesirable side-effects were observed.
EXample 9 : A room spray was prepared by dissolving 2 grams of polyvinyl pyrrolidone in 90 grams of isopropyl alcohol, 5 grams of triethylene glyccl and 3 grams of perfume oil. The solution containing the active substance was then used to fill containers while 15 grams of Frigen 11/12 ( a trade mark) and 7.5 grams of carbonic acid were added as propellant.

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Example 10 For the following tests, the person conducting the test held the spray container of Example 9 over the head and walked around the room to be treated. -(a) The smell of human feces in an especially serious case of pathological diarrhoea was removed rapidly and completely from a toilet, as well as the smell of a cat's feces from a room.
(b) The ef~ectiveness of the spraying composition against kitchen odours was tested with -~
(1) garlic,

(2) onions, (3~ sauerkraut, (4) radish salad, (5) strong-smelling cheese, and (6) stewed fish.
All odours disappeared completely.
(c) Tobacco smoke of any kind (cigarettes, cigars, pipe) was removed immediately and completely.

(d) The smell of garbage was removed spontaneously and lastingly from a waste-disposer shaft as well as from garbage cans and other containers.
(e) Rotting potatoes were sprayed and were then odourless. ;
(f) Liver was left to decay in a closed glass container.
When the liver was completely liquefied, the container was opened in the open air. Only persons having a rather insensitive stomach ~- ;
could approach the container. After spraying with the above composition, the container could be brought close to the nose, and no repulsive odour could be detected.

(g) After a room had been carpeted, an offensive odour remained which could be removed by spraying with the above com-position.
(h) A laboratory was sprayed with ammonia and formaldehyde, , .
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1~7~475 respectively, until the test persons showed serious irritations of eyes and respiratory tracts. The above spraying composition was then used and the persons left the room for 3 minutes. When entering again, they could only detect a slight perfumation of the air.
Example 11 A spraying composition for rooms and textiles was prepared by dissolving 5 parts of glycerol, 2 parts of polyvinyl pyrrolidone and 3 parts of perfume oil in 90 parts of isopropyl alcohol. The solution was then used to fill containers, adding 5 parts of carbon dioxide as propellant.
Example 12 The composition according to Example 11 was tested as follows:
(a) Heavy fuel oil, freshly cut onion rings and camphor, respectively, were placed upon the bottom of glass containers provided with a lid. ;
(b) Patches of coarse wool cloth having a size of about 1.5 sq. in. each, were suspended close above the surface of the test substance.
(c) After remaining in the containers for 2 hours, the cloth patches were removed and sprayed with the above composition.
(d) After 5 minutes in the open air, the patches were examined and proved completely odourless.
Example 13 Only one side of a wool sweater showing strong signs of perspiration was sprayed with the composition of Example 11.
The sweater was left in the open air over night. The treated side was then odourless while the other side still smelled "sweaty".
Example 14 ~ tablet against mouth and stomach odours was prepared -- 11 -- .
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by compressing 0.5 grams of polyvinyl pyrrolidone and 0.5 grams of sorbitol.
After drinking beer and eating fish, test persons took ~ -one tablet each and let it dissolve in the mouth. Bad breath was removed immediately. It a second test, the dissolved tablet was swallowed with some mineral water. In this way, even offen-sive odours arising from the stomach could be removed.
Example 15 The deodorizing spraying compositions of Examples 1 and 2 were used on about 100 test persons and resulted in spontaneous removal of perspiration odours from arm pits and feet. When treating one side of the test person with commercial products and the other side with a composition in accordance with the present invention, the compositions of the present invention proved superior with regard to compatibility and duration of the effect. Commercial products often caused allergic reactions ~ ~
and resulted in a reddening of the arm-pit; this was never the ~ ~ , case with the present compositions. They could even be applied ;-to already irritated parts of the body without interfering with the healing process. The effectiveness of the present composit-ions normally lasts two- to four-times longer with commercial products.
Example 16 A deodorizing body spray was prepared by dissolving 2 parts of polyvinyl pyrrolidone and 1 part of perfume oil in 92 parts of isopropyl alcohol. The solution containing the -active substance was then filled into containers under addition of 5 parts of carbon dioxide as propellant.

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~f~7~ 5 Example 17 Use of Polyvinylpyrrolidone (PVP) for the Protection of the Environment.
In the three following cases, PVP was employed for removing especially disagreeable and offensive odors.
(1) A side stream of collected exhaust air from a plant for the disposal of animal cadavers (Flaying house) was passed through a washing bottle filled up to a height of 3 centimeters with a 5 aqueous solution of PVP-60. By this simple measure, the "stink"
substances which, as a rule, are not soluble in water werespon-taneously, completely and permanently removed. The original PVP
solution remained effective over 4 days of 2 working shifts each, i.e. 16 working hours per day.
(2) At a plant located in a residential area, butyric acid was drained from a drum and 500 grams of the acid were spilled in the factory yard. Because of the annoying smell closing of the factory might have been anticipated. The offensive odor was completely removed by pouring a bucket of water containing a hand full of PVP-30 over the spot where the acid had been spilled.

(3) Five grams of PVP-60 were stirred into 1 liter of condensed steam from a flaying house, rendering the sewage completely odorless.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method of removing odors which comprises contacting an area affected with such odors with an effective amount of a composition comprising polyvinyl pyrrolidone, the said polyvinyl pyrrolidone having a molecular weight from about 5,000 to 2,000,000 which is soluble in water and alkanols containing up to three carbon atoms, the solutions thus produced having a k-value of from 5 to 150.

2. A method as claimed in claim 1, in which the polyvinyl pyrrolidone has an average molecular weight of from 10,000 to 1,000,000.

3. A method as claimed in claim 1, in which the polyvinyl pyrrolidone has an average molecular weight of from 13,000 to 450,000.

4. A method as claimed in claim 1, 2 or 3 in which the solution produced has a k-value of 10 to 95.

5. A method as claimed in claim 1, 2 or 3 in which the solution produced has a k-value of 13 to 35.

6. A method as claimed in claim 1 in which the compo-sition comprises a solution of polyvinyl pyrrolidone in at least one of water and an alcohol.

7. A method as claimed in claim 6, in which the alcohol has up to 6 carbon atoms.

8. A method as claimed in claim 6, in which the alcohol has 1 to 3 carbon atoms.

9. A method as claimed in claim 6, 7 or 8, in which the concentration of polyvinyl pyrrolidone is at least 0.1 % by weight based on the total weight of the solution.

10. A method as claimed in claim 6, 7 or 8, in which the concentration of polyvinyl pyrrolidone is 0.2 to 10.0 % by weight based on the total weight of the solution.

11. A method as claimed in claim 6, 7 or 8, in which the concentration of polyvinyl pyrrolidone is 0.3 to 3.0 % by weight based on the total weight of the solution.

12. A method as claimed in claim 1, in which the compo-sition comprises polyvinyl pyrrolidone in admixture with a solid carrier.

13. A method as claimed in claim 12, in which the weight ratio of polyvinyl pyrrolidone to carrier is from 25/75 to 75/25.

14. A method as claimed in claim 1, in which the compo-sition is a spray composition, a lotion or a tablet.

15. A method as claimed in claim 1, in which the odors are received from the air or the human body.

16. A deodorizing composition comprising a carrier and polyvinyl pyrrolidone, the said polyvinyl pyrrolidone having a molecular weight from about 5,000 to 2,000,000 which is soluble in water and alkanols containing up to three carbon atoms, the solutions thus produced having a k-value of from 5 to 150.

17. A composition as claimed in claim 16, in which is a solution of polyvinyl pyrrolidone in a solvent selected from water and an alcohol.

18. A composition as claimed in claim 17, in which the alcohol has up to 6 carbon atoms.

19. A composition as claimed in claim 16, in which the polyvinyl pyrrolidone has an average molecular weight of 10,000 to 1,000,000.

20. A composition as claimed in claim 16, in which the polyvinyl pyrrolidone has an average molecular weight of 13,000 to 45,000.

21. A composition as claimed in claim 16, 19 or 20 in which the solution is thus produced having a k-value of from 10 to 95.

22. A composition as claimed in claim 16, 19 or 20 in which the solution is thus produced having a k-value of from 13 to 35.

23. A composition as claimed in claim 16, 17 or 18, in the form of a spray composition in a container fitted with a spray nozzle.

24. A composition as claimed in claim 16, 17 or 18, in the form of a lotion including a dispersion base.

25. A composition as claimed in claim 16, 17 or 18, comprising about 0.1 to 75 parts by weight of polyvinyl pyrroli-done and 99.9 to 25 parts by weight of solvent.

26. A composition as claimed in claim 16, which is an admixture of polyvinyl pyrrolidone with a solid carrier.

27. A composition as claimed in claim 26 comprising about 0.1 to 99.9 parts by weight of polyvinyl pyrrolidone and about 99.9 to 0.1 parts by weight of carrier.

28. A composition as claimed in claim 26 or 27 in the form of a tablet.

29. A composition as claimed in claim 26 or 27 in which the carrier is a pharmaceutical or cosmetic carrier.