JPH04198122A - Thiol heterocyclic deodorizing composition and deodorizing method - Google Patents

Abstract

PURPOSE: To provide a deodorant composition that contains a specific thiol hetero ring compound and a topical carrier and is suitable for application to clothes which are put on skin or near skin and can inhibit the not-microbial, unpleasant smell accompanied by perspiration. CONSTITUTION: This deodorant composition comprises (A) a thiol heterocyclic compound that bears a hetero ring structure having at least one, preferably 1-3 hetero-atoms selected from O, N and S in the cyclic structure, particularly N atoms, has at least one thiol-substituent bonded to a C atom in the hetero ring and is unsubstituted other than the above-stated thiol substituted or substituted with OH, NH2 , an alkyl that may be substituted, preferably 2- mercaptopyridine, or 2-thiohystidine or ergothioneine, and (B) a topical carrier. The content of the component A ranges from 0.01 to 20wt.%, particularly from 0.5 to 2wt.%. The component A is preferably applied to skin, clothes or fabrics at a rate of 0.01-1.0mg/cm<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to compositions and methods for treating or preventing malodor associated with human sweating.

BACKGROUND OF THE INVENTION A vast amount of chemical, medical and cosmetological literature has been published regarding the causes, effects and prevention of human sweating.

"Sweat" or "sweat" is usually defined to include the excretion of sweat glands located in the dermis or subcutaneous tissue, known as ephrine sweat glands, which are distributed over most of the body's surface.

Although sweat serves an important function in cooling the body through its evaporation, the by-products resulting from its bacterial breakdown are malodorous and aesthetically unpleasant.

Malodor is particularly associated with sweat secreted in areas of the body where apocrine sweat glands are also found in addition to ephrine sweat glands.

The two main areas with apocrine sweat glands are the axilla or groin. For example, J.Labows,et al.+”P
erspectives on Axillary 0
dor” (perspectives on axillary odor), 34. J, Soc.
Cosmetic Chea+1sts, 193-20
2 (19B2) and P, Jacka+en, -Body
0dor-The Role of Skin Bac
terfa” (body odor – role of skin bacteria), 1°Sea+
fnars ln Dervatology, 143-
148 (1982).

A variety of bacteria are associated with axillary odor, and the main bacteria responsible for such malodor are Gram-positive bacterial flora naturally found in the axilla, such as Corynebacteria.
) and Propionibacteria (Propionibae)
diphtheritoids such as S. teria and Gram-positive cocci such as Staphylococcus and Micrococcus.

Various compositions have been developed and described in the literature for controlling or eliminating aesthetic problems associated with sweating.

For example, S,PIechner,-Antipersp
irants and Deodorants”, 2. Cosmetics.

5science and Technology, 37
3-416 (M, Balsam and E, Sagari
ed., 1972). Such compositions are commonly classified as antiperspirants that help stop or reduce sweat flow, fragrances that block unpleasant odors caused by sweat, and deodorants that stop or reduce the production of malodorous substances in sweat. be able to. Deodorizing compositions are preferred by many consumers for a variety of reasons.

For example, some individuals are unable to use commercial antiperspirant products due to sensitivity to the astringents typically used in these products.

Deodorizing compositions have been primarily conceived in the art for their role in halting or reducing the formation of bacterial byproducts in perspiration. This has been done through the use of antimicrobial agents that attack the bacteria responsible for producing malodorous byproducts.

Although these antimicrobial deodorizers were effective in reducing malodors, they did not completely eliminate the formation of malodor conditions. Therefore, it is desirable to provide a deodorizing composition that can further reduce malodors.

In addition, it is desirable to reduce malodor as soon as it forms. In some cases, malodors remain even after washing, for example in the armpit and crotch areas or in the armpit and crotch areas of clothing. Classically, already formed malodors were masked by fragrances. It would be desirable to provide improved methods and compositions for reducing malodors that remain after washing people or clothing. PCT published on July 30, 1987
In one approach, described in International Patent Application Publication No. WO 37/4341, axillary malodor is treated with cupric sulfate, silver sulfate, potassium permanganate, ferric chloride, sodium hydroxide, protein silver, and hypochlorite. sodium chlorate,
It is disclosed that it is neutralized by the use of zinc sulfate or copper gluconate.

However, it is desirable to provide alternative techniques for neutralizing malodors.

It is an object of the present invention to provide a composition effective in suppressing non-microbial malodor of human sweat. Another object of the present invention is to provide an effective method for suppressing non-microbial malodor of human sweat.

SUMMARY OF THE INVENTION The present invention provides compositions containing a thiol heterocyclic compound and a topical carrier for topical application to the skin of the axilla or crotch region or to clothing worn near such skin. Applicable deodorizers are thiol heterocyclic compounds having a heterocyclic structure with 5 to 10 heterocyclic atoms or pharmaceutically acceptable salts thereof;
is selected from the group consisting of oxygen, nitrogen, and sulfur, the remaining heterocycle atoms are carbon atoms, and the heterocycle further has at least one thiol substituent attached to the carbon atom of the heterocycle. There is.

DETAILED DESCRIPTION OF THE INVENTION It has been suggested that malodor formation and neutralization involve more than one mechanism, but such mechanisms are not completely understood. The inventors have demonstrated that even when sweat from the axillary or crotch regions of humans is disinfected so that virtually no viable bacteria remain that produce malodorous bacterial by-products, the sweat still produces an aesthetically objectionable malodor. I looked into Shiuroko.

Such malodors are hereinafter referred to as "non-microbial malodors." The inventors have determined that certain vitamin B6 compounds, normally secreted by human ephrine sweat glands, react to form non-microbial malodors when mixed with avocrine sweat gland secretions. The inventors have further determined that deodorizing compositions containing certain thiol heterocyclic compounds are highly effective in reducing such non-microbial malodors in human sweat.

These compositions are particularly useful in controlling the malodor associated with sweat associated with both avocrine and ephrin.

Additionally, such compositions are effective in reducing or preventing non-microbial malodors rapidly after such odors have formed.

It has been discovered that thiol heterocyclic compounds of the type described herein are highly effective in reducing the occurrence of malodorous sweat and deodorizing malodorous sweat. Non-microbial malodor increases over time, especially when sweat rates are high and times between washes are long. The concentration of non-microbial malodor precursors on the skin is thought to increase as more perspiration is secreted and the aqueous component of the already secreted perspiration evaporates, thus increasing the formation of recognizable non-microbial malodors. .

Without wishing to be bound by any theory, thiol heterocyclic compounds are derived from the aldehyde form of vitamin B6 (PLP).
) is thought to react with odor molecules produced from the interaction with sweat, reducing the volatility of odorants, thereby reducing their ability to reach the human olfactory organ.

The occurrence of such malodor conditions from non-microbial sources is substantially reduced by the thiol heterocyclic compounds of the present invention.

The compositions of the present invention include as essential ingredients a thiol heterocyclic compound that inhibits non-microbial malodor and a compatible carrier. As used herein, "suppressing non-microbial malodors" means reducing already formed non-microbial malodors to a level that is less perceptible to the human sense of smell and/or inhibiting the development of non-microbial malodors. . As used herein, "compatible" means that none of the components of the carrier react with the thiol heterocyclic compound such that the ability of the composition to suppress non-microbial malodors is substantially impaired. do.

The term "alkyl" as used herein means straight chain, branched or cyclic, substituted or unsubstituted, saturated, -
unsaturated (i.e., one double or triple bond in the chain) or polyunsaturated (e.g., two or more double bonds in the chain; two or more triple bonds in the chain; one or more double bonds in the chain; and one triple bond). As used herein, a saturated alkyl group is referred to as an "alkanyl," an unsaturated alkyl group with a double bond in the chain is referred to as an "alkenyl," and an unsaturated alkyl group with a triple bond in the chain is referred to as an "alkenyl." is referred to as “alkyninoji.” As used herein, “
The term “short chain alkyl” refers to 1 to about 6 carbon atoms in the chain.
means an alkyl having

The term "aryl" as used herein refers to a substituted or unsubstituted aryl group.

"Substituted aryl" means an aryl group having a substituent on the aryl ring. Examples of aryl are phenyl,
Naphthyl and substituted phenyl or naphthyl.

The term "substitution" as used herein means - or polysubstitution, especially -1 di- or tri-substitution.

Examples of substituents include halogen (in particular fluorine, chlorine or bromine), alkyl, hydroxy, amino, aryl (
In particular, phenyl or naphthyl), carboxylate, nitro, -CF3 and -ORCR are from about 1 to about 3 carbon atoms
(particularly methoxy and ethoxy).

Alkyl substituents are preferably C1-C6 alkyl, more preferably methyl or ethyl.

The de-irritating agent of the present invention has at least one atom in the ring structure,
That is, it is a thiol heterocyclic compound having a heterocyclic structure having a nitrogen, oxygen or sulfur atom and having a thiol substituent on the heterocyclic structure.

As used herein, "heterocyclic structure" refers to about 5 to
Refers to a covalent structure having about 8 rings, but may also have one or more other rings, and all rings are fused in the structure. “Condensation” as used herein
A ring is generally a ring having two or more ring atoms. The heterocyclic structure may be saturated, unsaturated, or partially or fully aromatic. Examples of heterocyclic compounds having oxygen, nitrogen and sulfur ring atoms can be found in CRC Handbook
ofChemistry and Physics,
57th edition, Robert C'Jeas
t,ed,,CRCPress,C1leveland,
0hio, pp, C-C-35through C-58, which is incorporated herein by reference.

The heterocyclic structure of the deodorants of the present invention preferably has about 5 to about 10 ring atoms, more preferably 5 or 6 ring atoms.

Preferably, 1 to 3 of the ring atoms are each independently selected from the group consisting of oxygen, nitrogen, and sulfur; 1 or 2 of the ring atoms are each independently selected from the group consisting of oxygen, nitrogen, and sulfur. It is even more preferable that 1 to 3 of the ring atoms are nitrogen; It is even more preferable that 1 or 2 of the ring atoms are nitrogen; The remainder is carbon. In a heterocyclic structure, ring heteroatoms are not directly bonded to other ring heteroatoms. The nitrogen atom of the ring structure does not directly bond to the oxygen atom to form an N-oxide.

The compositions of the present invention include a thiol heterocyclic compound having a single ring or multiple fused rings, where the thiol heterocyclic compound is a single heterocyclic structure having a thiol substituent or any of such fused ring structures. A heterocyclic structure having a thiol substituent located on the ring is preferred. Preferably, the thiol substituent on the fused ring structure is located on the heterocycle. Preferred fused ring structures have two 5- or 6-membered rings.

Thiol heterocyclic compounds have a single thiol substituent or multiple thiol substituents. Preferably, the thiol heterocyclic compound has about 4 or fewer thiol substituents, preferably 1 or 2 thiol substituents, and most preferably 1 thiol substituent.

The thiol-substituted heterocyclic structure of the thiol heterocyclic deodorant of the present invention may be unsubstituted (other than the thiol substituent) or may be further substituted. Other substituents of the above heterocyclic structure (
(other than thiol) is preferably attached to a carbon atom of the ring structure and is preferably selected from the group consisting of hydroxy, amino, substituted and unsubstituted alkyl. Preferred alkyls have 1 to about 8 carbon atoms, and more preferred alkyls are C1-Cs alkanyl and alkenyl. The nitrogen atom of the above heterocyclic structure may be substituted, but is preferably unsubstituted.

It is also preferred that at least one thiol substituent is attached to a carbon atom of a heterocycle having a delocalized electronic structure, examples of such carbon atoms include, but are not limited to, heteroaryl or ring rings. a carbon atom of a heterocycle double bonded to a nitrogen or sulfur atom of a heterocycle, a carbon atom of a heterocycle bonded to a nitrogen or sulfur atom of a heterocycle by a conjugated double bond, or an oxygen of a heterocycle Any carbon atom of the heterocycle is bonded to an atom or doubly bonded to a carbon atom of the heterocycle adjacent to the oxygen atom of the heterocycle. As used above, "bonded to a nitrogen or sulfur atom by a conjugated double bond" means that the heterocycle contains the following structural element: H -X-C-C-C- (X is S or N) It means that. Oxygen-containing heterocycles as described above include one of the following structural elements: In addition to the thiol heterocycle compounds described above, metal salts of such compounds are also included in the compositions of the present invention. These include, but are not limited to, the sodium, potassium, magnesium, zinc, aluminum, bismuth and lithium salts of the compounds. Preference is given to said compounds and their zinc, aluminum and bismuth salts.

Preferred deodorizing agents for use in the compositions of the invention are thiol derivatives of heterocyclic compounds of the following types: thiophenes, benzo[b]thiophenes, Natsuta C2,3-b).
Thiophenes, furans, bilanes, isobenzofurans, chromenes, pyrroles, imidazoles, pyrazoles, pyridines, pyrazines, pyrimidines, pyridazines, indolizines, isoindoles, indoles, purines , bovine noridines, isoquinolines, quinolines, phthalazines, naphthyridines, quinoxalines, quinozolines, cinnolines, pteridines, oxazolines, inthiazoles, oxazoles, isoxazoles and furazans. Preferred types of thiol derivative heterocyclic compounds include pyridines, pyrimidines, quinolines, and imidazoles. Imidazoles are particularly preferred.

More preferred deodorants used in the compositions of the present invention include 5,6-diamino-2-thiouracil, 1,5-diamino-6-hydroxy-2-mercaptopyrimidine, 4
．． 5-Diamino-6-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 2,4-diamino-6-mercaptopyrimidine hemisulfate, ergothioneine, 2-thiohistidine, 2-mercaptopyridine, 4-mercapto Pyridine, 2-mercaptobenzoxazole, 2-mercapto-6-nitrobenzothiazole, 2-thiocytosine, 6-thioxanthine, 2,6-dimercaptopyridine, 2-mercapto-5-nitropyridine, 2-mercaptoquinoline, 2 −
Mercapto-4-hydroxy-6,8-dichloroquinazoline, 4-mercaptoquinazoline, 2-phenyl-4-
Quinazolinthiol, 3-amino-6-methyl-4-pyridazinethiol, 5-amino-4-pyridazinethiol, α-tocopherthiol, 2-amino-6,7-dimethyl-4-pteridinethiol, 4-mercaptopteridine , 2-mercapto-4°-hydroxypteridine, and 2,4-diamino-6-phenyl-hupteridinethiol.

Even more preferred thiol derivative heterocyclic compounds include 2-mercaptopyridine, 4-mercaptopyridine,
These include 2,4-diamino-6-mercaptopyrimidine, 2-thiohistidine and ergothioneine. 2-thiohistidine and ergothioneine are particularly preferred.

The thiol heterocyclic compound applicable to the present invention is Sigma
Sigia CheIIIical Com
pany) [St. Louis, Missouri], Aldrich Chemical Co.
company) (Milwaukee, Rice Consin)
, K&K Laborato
ries) [Plainview, El.
] and P&B Research Chemicals.
[Waterbury, Connecticut]
ry) can be obtained commercially from industrial chemical sources such as ).

Preferably, the thiol heterocyclic deodorant does not react with components found in perspiration fluid in a manner that causes the thiol heterocyclic compound to appreciably malodor or to significantly reduce its effectiveness.

However, fragrances may also be added to the composition as an optional ingredient to mask the slight malodor of the thiol heterocyclic deodorizer and its reaction products.

The compositions of the present invention contain a safe and effective amount of a thiol heterocyclic compound when used as intended.

As used herein, a "safe and effective amount" is an amount that is effective in eliminating or substantially reducing non-microbial malodor, but is safe for the intended use with a reasonable benefit/risk ratio.

A2 Topical Compositions One aspect of the present invention is a deodorizing composition comprising a thiol heterocyclic compound and a topical carrier. The deodorizing compositions of the present invention comprising thiol heterocyclic compounds may be a variety of products that are applied topically to the skin or applied to clothing worn near the skin in normal use. Compositions formulated for topical application to the skin or designed for deposition on clothing and intended to continue to be deposited, at least initially, as the clothing is worn, contain a safe and effective amount of thiol heterocycle. Includes a topical carrier for depositing or releasing the compound and deodorant. As used herein, "applied to the skin" and "applied to the skin" refer to compositions in which deodorants are not typically deposited, such as skin cleaning compositions that are typically washed off after use. (described in more detail below) and its deposition on the skin such that the deodorant remains on the skin even after treatment of the skin with the composition.

The topical carrier for the deodorizing compositions of the present invention is in the form of a liquid, solid, cream, gel, lotion or other form and is preferably formulated to deposit the deodorant on the skin or clothing. As used herein, "deposited" and "deposited" of a deodorizing agent on the skin refers to the amount of deodorizing agent deposited on the skin after typical use of the deodorizing composition, even including a conventional deodorizing composition application step. means the application of a deodorizing composition to the skin such that it remains in the skin. Such topical carriers include, but are not limited to, conventional deodorizing compositions such as creams, sticks, roll-on liquids and spray liquids (including aerosols). skin lotions, skin conditioning, sunscreens and windscreens, sunscreens formulated as body lotions, creams and oils such as lotions and oils; skin cleansing products such as bar soaps, liquid soaps and cleaning gels; I have a career.

Typically, the topical deodorizing compositions of the present invention will contain from about 0.01 to
It contains about 20%, preferably about 0.05 to about 5%, more preferably about 0.5 to about 2% thiol heterocyclic deodorant.

Preferred deodorizing compositions of the present invention are conventional deodorizing compositions, including antiperspirant/deodorizing compositions formulated for topical application to the axillary region of the body or for application to the crotch region. The specific ingredients contained in the deodorizing compositions of the present invention will depend on the specific mode of application desired. These methods of application and the ingredients used in such compositions are well known in the art. A number of such compositions are described by S. Plechner, “Anti.
Perspirants and Deodorants
” (antiperspirant and deodorant), 2.Cos+++eti
cs.

5science and Technology, 37
g-416 (M, Ba1sa* and E, Sagarfn
ed, 1972), which is incorporated herein by reference.

The topical carrier for deodorizing compositions primarily formulated for the deposition of thiol heterocyclic deodorants on the skin of the axillary area for malodor control preferably contains no more than about 5% water, more preferably no more than about 2% water. of water, most preferably essentially 0% water. Other compositions may contain large amounts of water, and the presence of water is not expected to affect the efficacy of the thiol heterocyclic deodorant.

Topical carriers useful for depositing thiol heterocyclic deodorants on the skin in the form of creams, ointments, lotions, oil-in-water and water-in-oil emulsions are known in the art and are known in the art, e.g. Water-in-oil emulsions disclosed in U.S. Pat. No. 4,254,105 issued to Fakuda et al. F
There are three-phase emulsion carrier systems, such as the silicone oil-in-liquid-in-water emulsions disclosed in European Patent Application No. 281,394 to J. Gueroa et al., incorporated herein by reference.

1. Liquid compositions useful in this invention, such as roll-ons, sprays, and aerosols, preferably contain a liquid emollient as all or a substantial portion of the topical carrier. Such compositions are suitable for delivery from conventional roll-on, spray and aerosol containers (respectively) known in the art. Such emollients include fatty acid and fatty alcohol esters, water-insoluble ethers and alcohols, polyorganosilicones, and mixtures thereof. Polyorganosilicone is one of the preferred emollients useful herein. Liquid topical carriers are disclosed in the following patent specification, which is incorporated herein by reference;
U.S. Patent No. 4,053,851 issued to Ader et al.
No. 4,065,564 issued to Miles, Jr., et al., December 27, 1977;
No. 4,073,880 issued to Pader et al. on February 14, 1981;
U.S. Patent Section 4.278,655 issued to lll;
British Patent Application Box 2,018,590 to Elmi, published October 24, 1979; and European Patent Application Box 28,853, published to Beckmeyer et al., July 11, 1984.

The liquid deodorizing compositions of the present invention may also contain alcohols and/or polyols as a substantial component of the topical carrier. Alcohols useful herein include ethanol, propatool, impropatool, and mixtures thereof. Polyols useful here include glycols such as propylene glycol.

The liquid composition may also contain fillers to modify the physical and/or cosmetic characteristics of the composition. Such fillers are typically present at levels of about 1% to about 8%. Bulking agents useful herein include talc, colloidal silica, clays, and mixtures thereof.

2. Aerosols The aerosol compositions of the present invention contain one or more volatile substances, i.e. herein "
Contains propellant. Aerosol propellants useful herein typically have boiling points within the range of about -45°C to about 5°C. Aerosol propellants are liquefied when filled into a conventional aerosol container under pressure. The rapid boiling of the aerosol propellant upon exiting the aerosol container aids in atomization of the other components of the aerosol composition.

Aerosol propellants useful herein include those well known in the art. Suitable aerosol propellants include chemically inert hydrocarbons such as propane, n-butane, isobutane, cyclopropane and mixtures thereof, as well as halogenated hydrocarbons such as dichlorodifluoromethane (propellant 12). ), 1,1-dichloro-1,1,
2,2-tetrafluoroethane (propellant 114), 1-
Chloro-1,1-difluoro-2,2,2-trifluoroethane (propellant 115), 1-chloro-1°1-difluoroethylene (propellant 142B), 1°1-difluoroethane (propellant 152A), Monochlorodifluoromethane (propellant 22) and mixtures thereof. Isobutane, used alone or mixed with other hydrocarbons, is preferred for the aerosol compositions of the invention.

3. Deodorizing Stick The solid composition of the present invention is in stick form as known in the art, typically comprising a liquid base material and a coagulating agent. These deodorizing sticks are commonly described as either gel sticks or wax sticks, depending on the specific liquid base material and coagulant used.

Generally, the liquid base material is present at a level of about 10% to about 97%. Coagulants are typically present at levels of about 1% to about 7%.

As will be apparent to those skilled in the art, the selection of a particular liquid base material and the selection of an appropriate coagulant will vary depending on the particular type and rheology desired.

Various liquid base materials and coagulants useful herein, as well as sticks made from these materials, are described in the following documents, all of which are incorporated herein by reference: S., PIechner.

”Antiperspirants and Deod
orants'' (antiperspirant and deodorant), 2.Co5Il
rhetics, 5science and techno
Logy.

373-416 (M, Ba1saa+ and E, Sag
Arin ed, 1972); C.

Fox, “Gel and 5ticks Revie”
w and Update- (Considerations and latest information on gels and sticks), 99°Cosmetics & T
ofletrfes, 19-52 (1984); N, G
erla, “Formulation of 5tic
k Antiperspirants and Deod
orants” (Stick antiperspirant and deodorant formulation)
, 99. Co5a+etics & Toiletrj
es, 55-99 (1984);
and 5ticks Formulary- (gel and stick formulation), 99. Co511etics &
Toiletries, 77-87 (1984)
.

The liquid base materials used in wax deodorant sticks usually also function as emollients, improving the cosmetic acceptability of the deodorant stick. Such emollients include fatty acid and fatty alcohol esters, water-insoluble ethers and alcohols, polyorganosiloxanes, and mixtures thereof. Polyorganosiloxane is one of the preferred liquid base materials useful in the Fuchs deodorizing sticks of the present invention.

Coagulants useful in the wax deodorizing sticks of the present invention are wax materials, typically incorporated at levels of about 5 to about 50%. Wax materials useful herein are high melting waxes having melting points of about 62-102°C.

Low melting waxes having melting points of about 37-75°C are also preferred. Such low melting waxes include fatty acids, fatty alcohols, fatty acid esters, fatty acid amides and mixtures thereof. Stearyl alcohol, cetyl alcohol and mixtures thereof are also particularly preferred wax materials useful in the deodorizing stick compositions of the present invention. Liquid base materials and coagulants among those useful in the wax-type deodorizing sticks of the present invention are disclosed in the following U.S. Patent No. 197, incorporated herein by reference:
No. 4,049.792, issued September 20, 1977;
U.S. Patent No. 4,151.272 issued to Early et al.
No. 4,299,432 issued to Geria on October 21, 1980; July 2, 1981
U.S. Patent No. 4,28 issued to Turney on 8th.
No. 0,994, U.S. Pat. No. 4,126,679 issued to Davy et al., Nov. 21, 1978;
May European Patent Application No. 117.070, published August 29, 1984.

The gel deodorizing stick of the present invention contains a liquid base material selected to also exhibit desirable cosmetic properties, such as emollient properties and/or a cooling sensation when applied to the skin. Liquid base materials useful in such gel sticks include water, lower-hydric alcohols, polyhydric alcohols, and mixtures thereof. Such substances include ethanol, isopropanol, n-propanol, n-
Butanol, isobutanol, t-butanol, ethylene glycol, propylene glycol, trimethylene glycol, glycerin, 1,3-butanediol, 1,
4-butanediol and mixtures thereof. Ethanol, propylene glycol and mixtures thereof are preferred liquid base materials for the gel sticks of the present invention.

Coagulating agents useful in the gel deodorizing sticks of the present invention are generally surface-active compounds that solidify or coagulate the liquid-based material into a gel to form a network. Such coagulants typically include soaps, higher fatty acid amides of alkylamines, benzylidene sorbitol, propionates and lactates, waxes and mixtures thereof. The preferred coagulant for the gel deodorizing stick of the present invention is nonionic in nature. A preferred coagulant useful in the gel deodorizing sticks of the present invention is benzylidene sorbitol, particularly dibenzaldehyde monosorbitol acetal. Such materials come from a variety of sources, e.g.
D (Gell^II-DTM) (Shin Nippon Chemical Co., Ltd.)
New Japan Chemical Company
y, Ltd.] and Millithix (Millith
ixTM) (Miliken Chemical Division of Milliken & Company)
, Divfsion of Millken & Co.
It is commercially available as [manufactured by mpany]. Liquid base materials and coagulants useful in the gel-type deodorizing sticks of the present invention are disclosed in the following patent specification: 1.959/8, all of which are incorporated herein by reference.
US Patent No. 2, issued on May 18th, 5later.
Barto No. 900,306, June 7, 1966.
U.S. Patent No. 3.255.082, 19, issued to n.
US Pat. No. 4,137.306 issued to Rubino et al. on January 30, 1979; US Pat.
No. 816; U.S. Pat. No. 4,226,889 issued to Yuhas on Oct. 7, 1980; U.S. Pat.
, No. 3'46,079, dated May 17, 1983, Ta
U.S. Patent No. 4,383,988 issued to ng et al.;
U.S. Patent No. 4,504,465 issued to 5arApson et al. on March 12, 1985, European Patent Application No. 1 to Luebbe et al., published on May 2, 1984.
No. 07,330; and U.S. Pat. No. 4,816,261 issued to Luebbe et al. in 1989.

A preferred gel stick formulated with benzylidene sorbitol and cetyl alcohol is disclosed in U.S. Pat. No. 4.743, issued to McCall on May 10, 1988;
No. 444 (incorporated herein by reference)
It is written in.

The deodorizing sticks of the invention, especially wax type deodorizing sticks, may contain inert filler substances. Such materials include talc, colloidal silica [e.g.
n) Cab-0-8i for sale
lo)), clays (eg bentonite) and mixtures thereof. Such filler substances are 197
U.S. Pat. No. 117,070, incorporated herein by reference.

Deodorizing compositions of the present invention that are applied topically to the skin may, in addition to the thiol heterocyclic deodorants of the present invention, also contain optional ingredients that function as additional "active" ingredients when deposited on the skin. However, it is preferred that such additional active ingredients do not substantially interfere with the deodorizing activity of the thiol heterocycle. Active ingredients are not particularly limited, antibacterial agents,
Examples include bactericides and fungicides, and other deodorants such as antiperspirants. The active ingredient must be stable in the formulation of the composition. Preferably, a "safe and effective amount" of the active ingredient is used. Various active ingredients among those useful in the present invention are described in U.S. Pat. ing.

Preferred antiperspirant materials useful in the deodorizing compositions of the present invention include aluminum and zirconium salts such as aluminum halides, aluminum hydroxyhalides, oxidized zirconylno\lides, zirconylhydroxyno\lides, and mixtures thereof. Among those useful here are antiperspirants published by Beckmeyer on July 11, 1984.
European Patent Application No. 28,853 (
(incorporated herein by reference). Such materials are typically included at a level of about 15% to about 40%, based on the total weight of the composition.

Other optional antiperspirants include U.S. Patent No. 4.226,8 issued to Paclvan on October 7, 1980
No. 50 Specification and Pack dated November 18, 1980
No. 4,234,566 issued to +wan, both incorporated herein by reference.
There are antihistamines selected from the group of ethanolamines, ethylenediamines, alkylamines, phenothiazines and piperazines, or pharmaceutically acceptable salts thereof, as described in . Still other optional antiperspirants include U.S. Pat.
No. 3,326°768, issued June 20, 1967, to MacMi I fan, 197
U.S. Pat.
Various belladonna alkaloids such as the esters of scopolamine and atropine described in U.S. Pat. There are anticholinergic agents.

As will be appreciated by those skilled in the art, certain antiperspirant substances described above may be ineffective in or destabilize the compositions of the present invention. Thus, the compositions of the present invention may contain a buffering agent to maintain a pH of at least about 6.0 in the composition. Such buffers were introduced in 1979.
No. 4,154°816 issued to Roehl et al. on May 15, 1982; U.S. Pat. No. 4,346 issued to Roeh I on August 24, 1982;
No. 079 specification; and as of May 21, 1985, Sch.
U.S. Patent No. 4.51g issued to amper et al.

No. 582, all of which are incorporated herein by reference.

Some preferred compositions of the invention also contain safe amounts of deodorants other than thiol heterocyclic deodorants, such as antimicrobial agents (eg, bactericides and fungicides) or mixtures thereof. Such other deodorants (by weight of the composition) contain about 0
．． Usually present at levels of 1-10%. Other suitable deodorizers include cetyltrimethylammonium bromide,
Cetylpyridinium chloride, benzethonium chloride, diisobutylphenoxyethoxyethyldimethylbenzylammonium chloride, N-laurylsarcosine sodium, N-polymethylsarcosine sodium, lauroylsarcosine, N-myristoylglycine, N-lauroylsarcosine potassium, stearyltrimethylammonium chloride and their There are mixtures of bacteriostatic quaternary ammonium compounds. Other suitable deodorizers include 2.4.4"4-lichloro-2'-hydroxydiphenyl ether, zinc pyrithione (ZPT), and sodium bicarbonate. Other particularly preferred deodorizers include:
diaminoalkylamides, such as monolysine hexadecylamide, described in U.S. Pat. There is.

Other optional ingredients of the deodorizing composition of the present invention include fragrances, pigments, dyes, colorants, and ultraviolet absorbers.

The deodorizing compositions of the present invention are manufactured by various techniques well known in the art. For example, such techniques for producing solid deodorizing compositions are described in "Gets and SticksFor
mulary” (gel and stick formulation), 99°C
o5IIletics & Toiletries, 7
7-87 (1984), which is incorporated herein by reference.

4. Creams, Ointments and Lotions The cream, ointment and lotion compositions of the present invention typically include one or more emollients as a component of the topical carrier. As used herein, "emollient" refers to substances used to prevent or reduce dryness and protect the skin. A variety of suitable emollients are known and can be used in the present invention. Sagari, which is incorporated herein by reference.
n, Cosmetics, 5science and T
technology, 2nd Edition, Vol.
, 1. pp. 32-43 <1972) contains various examples of suitable materials. Examples of useful emollient types include secondary hydrogenated oils and waxes; silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, water-soluble and alcohol-soluble silicone glycol copolymers; vegetable and animal fats and oils; triglyceride esters such as; acetoglyceride esters such as acetylated monoglycerides; ethoxylated glycerides such as ethoxylated glyceryl monostearate; alkyl esters of fatty acids having 10 to 2° carbon atoms; 10 to 2 carbon atoms
alkenyl esters of fatty acids having 0; carbon atoms 10
fatty alcohols having from 10 to 20 carbon atoms; fatty alcohol esters; ether-esters such as ethoxylated fatty alcohol fatty acid esters; lanolin and derivatives: polyhydric alcohols and polyether derivatives; polyhydric alcohol esters; Wax esters such as beeswax, spermaceti, myristyl myristate, stearyl stearate; beeswax derivatives; vegetable waxes such as carnauba and candelilla wax; phospholipids such as lecithin and derivatives; cholesterol and cholesterol fatty acid esters sterols; amides such as fatty acid amides, ethoxylated fatty acid amides, solid fatty acid alkanolamides.

Particularly useful emollients that provide skin conditioning are glycerol, hexanetriol, butanetriol, lactic acid and its salts, urea, pyrrolidone carboxylic acid and its salts, amino acids, guanidine, diglycerol, and triglycerol.

The lotion of the present invention in solution form typically has a concentration of about 0.01
~20%, preferably about 0. 1 to about 5% thiol heterocyclic deodorant; about 1 to about 20%, preferably about 5 to about 10% emollient; about 50 to about 90%, preferably about 60 to about 80% water; include. Creams of the invention in solution form typically contain from about 0.01 to about 20%, preferably about 0.
．． 1 to about 5% thiol heterocyclic deodorant; about 5 to about 50%
%, preferably about 10 to about 20% emollient; about 45
Contains up to about 85% water, preferably about 50 to about 75% water.

The ointments of the present invention contain a single base of animal or vegetable oil or semi-solid hydrocarbon (oily). The ointment may also include an absorbent ointment base that absorbs water to form an emulsion. Examples of such ointment bases are anhydrous lanolin and hydrophilic petrolatum. Emulsion ointment bases may be oil-in-water or water-in-oil emulsions. Ointment carriers may also be water soluble. Examples of such ointment carriers include ingredients such as glycol ethers, propylene glycol, polyoxylstearates and polysorbates. Ointments typically contain about 2% to about 10% emollient and about 0.1% to about 2% thickener. A more detailed disclosure of thickening agents useful herein is provided by Segarin, Cosmet
ics, 5science and Technology
y.

2r+dEdftfon, Vol, 1. pp, 72-7
3 (1972), which is incorporated herein by reference.

When the topical carrier of the present invention is formulated as an emulsion, typically about 1% to about 10%, preferably about 2% to about 5% of the carrier is an emulsifier.

The emulsifier may be nonionic, anionic or cationic. Suitable emulsifiers are e.g.
No. 3, issued to Dickert et al.
No. 755,560; U.S. Pat. No. 4,421,76 issued to Dixon et al. on December 20, 1983.
Specification No. 9; and MeCutcheon's, Dete
rgents and emulsifiers.

North American Edjon, pa.
ges 317-324 (198B), the disclosures of which are incorporated herein by reference. Preferred emulsifiers are anionic or nonionic, although other types can also be used.

Single emulsion skin care formulations such as oil-in-water and water-in-oil lotions and creams are well known in the cosmetic industry and are also useful in the present invention. Multiphase emulsion compositions such as the water-in-oil-in-water type disclosed in U.S. Pat. No. 4,254,105 issued to Fakuda et al. are also useful in the present invention. Generally, such single or multiphase emulsions contain water, emollients and emulsifiers as essential ingredients.

Also useful in the present invention are three-phase emulsion carriers containing the silicone oil-in-water emulsion compositions disclosed in European Patent Application Box 281,394 (noted above). More specifically, such a three-phase emulsion carrier system comprises: a) a silicone liquid continuous phase consisting essentially of at least one liquid organopolysiloxane;
b) from about 30% to about 80% by weight (in the vehicle) of an aqueous discontinuous phase comprising an oil-in-water emulsion of a cosmetically acceptable oily liquid non-particulate phase dispersed in a liquid phase; and c) An effective dispersion of about 0.5 to about 5 weight percent dimethicone copolyol (in the vehicle) to disperse (b) in (a).

Another emulsion carrier useful in the compositions of the invention is a macroemulsion carrier.

Such carriers include about 9% to about 15% squalane, about 25% to about 40% silicone oil, about 8% to about 20% fatty alcohol, and about 15% to about 30% polyoxyethylene sorbitan monofatty acid [trade name Tweeno
] or other nonionic substances and about 7 to about 20%
Contains water.

Lotions and creams can be formulated as emulsions and solutions. Typically, such lotions in emulsion form contain from about 0.01 to about 20%, preferably from about 0.1 to about 5%, of the thiol heterocyclic deodorant; about 1
~ about 20%, preferably about 5 to about 10% emollient;
about 25 to about 75%, preferably about 45 to about 95% water;
and about 1 to about 10%, preferably about 2 to about 5% emulsifier. Such reams in emulsion form typically range from about 0.01 to about 20%, preferably from about 0.1 to about 5%
% thiol heterocyclic deodorant; about 1 to about 20%, preferably about 5 to about 10% emollient; about 20 to about 80%;
Preferably about 30 to about 70% water; and about 1 to about 10%
, preferably from about 2 to about 5% emulsifier.

5. Skin Cleansing In addition to the above deodorizing composition, the deodorizing composition of the present invention includes a skin cleansing deodorizing composition, which comprises a thiol heterocyclic compound and a safe and effective amount of a surfactant for topical application to human skin. and a topical carrier containing the agent. The term "a safe and effective amount of surfactant for topical application to human skin" refers to a surfactant that is not only an effective skin cleanser, but also can be used without undue toxicity, irritation, allergic reactions, etc. The skin cleansing deodorizing compositions of the present invention preferably contain from about 0.01 to about 20% thiol heterocyclic deodorant and from about 1 to about 90%, preferably from about 50 to
Approximately 90% of human skin topical applications contain surfactants.

The physical form of the skin cleansing deodorizing composition is not important. The composition can be formulated, for example, as a cosmetic solid, liquid, paste or mousse. The cosmetic solid body is
This is most preferred as it is the most commonly used form of cleansing agent for cleaning the skin.

Those skilled in the art will appreciate that active ingredients applied to the skin from skin cleansing compositions may not typically be significantly deposited on the skin due to factors such as washing after application of such products. Probably. Even if significant deposition of thiol heterocycles on the skin is not achieved, the composition is still highly effective in controlling non-microbial malodor already formed in the axillary or crotch areas. Non-microbial malodor control when combined with skin cleansing compositions is particularly beneficial since malodorous skin conditions may remain even after the affected axillary and crotch areas have been cleaned with conventional skin cleansing compositions. Show great profits.

Safe and effective amounts of surfactants compatible with the thiol heterocyclic deodorizer, such as surfactants selected from anionic, nonionic, zwitterionic, amphoteric, ampholyte surfactants and mixtures of these surfactants, are also included in the present invention. Can be used in compositions. Such surfactants are well known to those skilled in the detergent industry. Suitable surfactants are for example McC
Utcheon's.

Detergents and Emulsjfier
s, North American Ed, pages
317-324 (1988). It is not believed that the particular surfactant is important in obtaining the antimicrobial malodor effect of the present invention.

The skin cleansing and deodorizing composition of the present invention comprises the above substances,
Antibacterial and fungicidal agents further comprising the materials described in U.S. Pat. such as the above-mentioned materials, and also mineral oil, about 1
paraffin wax having a melting point of from 0.00 to about 170;
fatty sorbitan esters (see U.S. Pat. No. 3,988,255, issued to 5eiden, Oct. 26, 1976, incorporated herein by reference);
Emollients including lanolin and lanolin derivatives, esters such as isopropyl myristate, triglycerides such as coconut oil or hydrogenated tallow; to improve the volume and quality (creaminess) of the lather produced with the composition; Free fatty acids such as coconut fatty acids, preferably at a level of about 10% or less: fragrances, dyes, pigments, polymeric skin sensitizers [e.g., Hoechst Celanese
Jaguar (J) manufactured by stCelanese Corp.
aguar) C-14-S], humectants, thickeners, preservatives, alkali agents, propoxylated glycerol derivatives skin conditioning agents or other cosmetic adjuvants. It may optionally contain materials conventionally used in skin cleansing compositions, including ingredients at their art-established levels.

Skin cleansing compositions formulated as cosmetic bar soaps usually contain from about 50 to about 90% surfactant. Moisture is usually present at a level of about 5% to about 20%. Skin cleansing compositions formulated as liquids typically contain about 10 to
Contains about 30% surfactant and about 60 to about 90% water. Skin cleansing compositions formulated as pastes usually contain about 20 to about 60% surfactant and about 30 to about 50% water. Pastes and liquids usually also contain organic thickeners such as natural rubbers and polymers.

An example of a soap-based cosmetic bar composition is U.S. Pat. No. 3,567 issued to Megson et al. on April 27, 1971.
．． No. 749, which is incorporated herein by reference. Examples of synthetic base cosmetic solids that can be used in preparing the compositions of the invention include: June 6, 1961
No. 2, issued to Lundberg et al.
No. 987,484, which is incorporated herein by reference. Other examples of soap/synthetic based cosmetic solids are Chaf'f dated December 25, 1962.
No. 3,070,547 issued to 'ee and U.S. Patent No. 3,376.229 issued April 2, 1967 to Haas et al. is incorporated herein by reference. Examples of soap-based liquid cleansing compositions that can be used in preparing the liquid compositions of the present invention include
U.S. Patent No. 4,310,4 issued to ti ros
No. 33, which is incorporated herein by reference.

Examples of synthetic-based liquid cleansing compositions that can be used in preparing the compositions of the present invention include
U.S. Patent No. 4,338.211 issued to tiros
No. 3, which is incorporated herein by reference. Paste compositions are described in U.S. Pat. No. 4,310,433 and U.S. Pat.
．． No. 338,211 by appropriate reduction of the level of water in the composition of No. 338,211. Examples of ultra-mild skin cleansing compositions that can be used in making the compositions of the present invention are found in U.S. Pat. No. 4,673,525, issued June 16, 1987, to Small et al. , which is incorporated herein by reference. Examples of skin cleansing mousse compositions containing ethoxylated nonionic and wholly or partially esterified polyol nonionic surfactants and also having skin conditioning ingredients such as emollients and skin moisturizers are published in December 1987.
U.S. Patent No. 4, issued to 5nyder on May 14th,
No. 708.813, which is incorporated herein by reference. In addition to disclosing examples of skin cleansing compositions of the present invention, the above-incorporated patent specifications describe various surfactants that can be used in the compositions of the present invention, including soap-based and detergent-based surfactants. It also discloses agents. The skin cleansing deodorizing composition of the present invention is produced by blending a thiol heterocyclic deodorizing agent into the same composition as above.

B. Laundry Product Compositions Another aspect of the present invention relates to laundry product compositions comprising the thiol heterocyclic deodorizers of the present invention and laundry product carriers. Carriers for laundry products can be in liquid, granular or solid form and contain liquid and granular detergents and wash additive, rinse additive and dryer additive substrates, which may contain other additives such as fabric conditioning and/or detergent ingredients. It may also contain the following ingredients. Laundry product compositions include thiol heterocyclic deodorizers that deodorize and wash or rinse away clothing (odor removal) or deposited on clothing to control non-microbial odors (odor prevention) during the washing step. It is prescribed in either to leave a residue.

The laundry product compositions of the present invention are believed to be particularly beneficial in reducing non-microbial malodor substances adsorbed onto fabrics.

Typically, such laundry product compositions contain about 0.001
Contains ~20% thiol heterocyclic deodorant. Laundry product compositions formulated for odor removal preferably contain about 0.
001 to about 1%, more preferably about 0.005 to about 0.001% to about 1%.
5%, even more preferably from about 0.01 to about 0.1% thiol heterocyclic deodorant. Laundry product compositions formulated for odor prevention preferably contain from about 0.01 to about 10%
, more preferably from about 0.1% to about 5% thiol heterocyclic deodorant.

As used herein, "laundry product compositions" include compositions such as liquid and granular detergents, liquid and granular fabric conditioning, and washer or dryer additive substrates, which include fabric conditioning and/or detergent ingredients. It may also contain.

Such compositions include the thiol heterocyclic deodorant of the present invention, but typically also include one or more of the following ingredients:

Cleaning Surfactant 2 The detergent composition of the present invention contains an organic surfactant ("surfactant") to provide the usual cleaning effects associated with the use of such products.

Detergent surfactants useful herein include the well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical examples of these are alkylbenzene sulfonates,
Alkyl and alkyl ether sulfates, paraffin sulfonates, olefin sulfonates, amine oxides, α-sulfonates of fatty acids and fatty acid esters, alkyl glycosides, ethoxylated alcohols and ethoxylated alkyl phenols, etc., are well known in the detergent industry. Generally, such detersive surfactants have alkyl groups in the C9-018 range, or anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts.

Standard texts such as McCutcheon's Index contain detailed lists of such typical detersive surfactants. C11-014 alkylbenzene sulfonates, Cl2-C1,8 paraffin sulfonates, C11-C18 alkino sulphates and alkyl ether sulfates are particularly preferred in compositions of this type.

Water-soluble soaps such as common sodium and potassium coconut or tallow soaps well known in the art are also useful herein.

Unsaturated soaps such as alkyl soaps may also be used, especially in liquid formulations. Saturated or unsaturated Cc+-Cie hydrocarbyl succinates are also effective.

with anionic substances such as alkylbenzene sulfonates, alkyl sulfates and paraffin sulfonates.
The mixture with 9-C1B engineered toxylated alcohol surfactant removes a broad spectrum of soil and dirt from fabrics through-the-wash.
h) Preferred for cleansing.

Combinations of anionic, cationic and nonionic surfactants can also commonly be used. Such combinations or combinations of anionic and nonionic surfactants alone are also preferred for liquid detergent compositions. Such surfactants are commonly used in acid form and are neutralized during the manufacture of liquid detergent compositions. Preferred anionic surfactants for liquid detergent compositions include linear alkylbenzene sulfonates, alkyl sulfates, and alkyl ethoxylated sulfates. Preferred nonionic surfactants include alkyl polyethoxylated alcohols.

Anionic surfactants are preferred for use as detersive surfactants in granular detergent compositions. Preferred anionic surfactants include linear alkylbenzene sulfonates and alkyl sulfates. Combinations of anionic and nonionic detersive surfactants are also particularly useful for granular detergent applications.

Detergent compositions typically contain from about 10 to about 60% water-soluble detersive surfactant. Suitable surfactant and detergent compositions are described in Laugh Li, December 30, 1975.
No. 3,929,678 issued to n et al. and U.S. Pat. Both are incorporated herein by reference.

Conventional Builders2 Builders used in the practice of this invention include various sequestering agents such as amine chelators and phosphonate chelators, alkylene aminophosphonates such as diethylenetriaminepentaacetic acid, ethylenediaminetetraphosphonic acid, and There are tripolyphosphates as well as "pyro" builders well known in the art. Importantly, a variety of non-phosphorous builders can be used. For example, but not limited to these, 1 to 10
μ Zeolite A (Zeolite A), 2. 2'
- oxodisuccinates, tartrate mono- and disuccinates, citrates, C8-014 hydrocarbyl succinates, sodium carbonate and mixtures thereof. Inorganic salts such as sodium sulfate may also be present.

A list of builders useful herein can be found in the above-cited US Pat. No. 4,704,233.

Bleach: A variety of well-known bleaching agents (particularly fiber and fabric bleaches) are well known and can be used as components of carriers for laundry products. Sodium perborate and tetrahydrate are preferred for laundry products, but percarbonates and persulfates are also useful. Aqueous hypochlorite is also a routine additive in many laundry operations. As mentioned above,
Bleaching agents useful as a component of the compositions of this invention are limited to those that are compatible with the thiol heterocycle compounds in the compositions.

Detergent adjuvant compositions can contain a variety of ingredients to aid their cleaning performance. For example, the laundry compositions preferably also contain enzymes to enhance their through-the-wash cleaning performance on various soils and soils. Amylase and protease enzymes suitable for detergent applications are well known in the art and in commercial liquid and granular detergents. Commercially available detergent enzymes (preferably amylases and proteases) are typically used in the present compositions at levels of 0.001-2% and higher.

Furthermore, in addition to the above ingredients, the compositions can also contain various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH adjusters, fragrances, dyes, bleaches, fluorescent brighteners, polyester soil release agents, hydrotropes, gel control agents, freeze-thaw stabilizers, fungicides, preservatives, and foam control agents. , bleach accelerators, etc.

Fabric softeners, particularly clays and mixtures of clays with various amines and quaternary ammonium compounds, can all be used in the present compositions. Such matters are well known from the patent literature and from commercial practice.

The compositions are manufactured using conventional techniques well known to formulators of commercial detergent and bleach products.

Fabric conditioning agents, when present in laundry product compositions, typically range from about 1% to about 35%, preferably from about 6% to about 25% of the composition. The specific fabric conditioning agent utilized is not believed to be critical to the invention, and any fabric conditioning agent known in the art is believed to be applicable. These include, for example, 19
Quaternary ammonium fabric conditioners as disclosed in U.S. Patent No. 3,936,537, issued to Bakervill Ie et al.
Tertiary amines as disclosed in UK Patent No. 1,514,276 to Kenyon, published June 14, 1978; assigned to Bayer, July 1977;
British Patent No. 1.077.103 published on the 26th of May
1,077.104 and U.S. Patent Application No. 153,172 of Ca5vel I filed February 8, 1988; 1977 5to as of December 13th
U.S. Patent No. 4,062,647 issued to rn et al. and British Patent Nos. 1 and 4 assigned to Procter & Gamble and published August 24, 1977.
There are smectite 9-ib clay flexible systems, such as those described in US Pat. No. 83,627.

Aqueous dispersions useful for direct application to garments in aerosol form include a thiol heterocyclic deodorant, about 0.1 to 10% water, about 0.01 to about 5% a suitable organic solvent, and the balance as appropriate. Contains propellant i. Examples of such propellants are chlorinated,
Fluorinated and chlorofluorinated low molecular weight hydrocarbons.

Nitrogen oxide, carbon dioxide, isobutane and propane can also be used as propellant gases. These propellants are used at levels sufficient to propel the contents of the container. Suitable organic materials useful as a solvent or part of a solvent system are: propylene glycol, polyethylene glycol (CM, W, 200-600), polypropylene glycol (M, W).

425-2025), glycerin, sorbitol ester, 1. 2. 6-hexandriol, diethyl tartrate, butanediol and mixtures thereof. The balance of the composition is a liquid carrier, preferably the carrier is water or a mixture of water and a -hydric alcohol.

Liquid fabric treatment compositions can be prepared by mixing the thiol heterocyclic deodorizer alone or with other ingredients in a solvent.

The deodorizer of the present invention can be added to the granule carrier by mixing the deodorant with the other composition components in solution before being spray-dried, and then spray-drying the mixture in a conventional manner. Alternatively, granular or powdered laundry product compositions may be prepared by triblending the deodorizer with other composition ingredients.

C1 Fabric Treatment Composition Another aspect of the invention is a fabric treatment composition comprising a thiol heterocyclic agent of the invention and a fabric treatment carrier for deposition onto clothing or fabrics worn close to the skin. Regarding. A "fabric processing carrier" as used herein typically includes one or more of the following ingredients: a fluorescent brightener, a surfactant (preferably nonionic or ionic), or an organic ester. It is believed that the fabric treatment composition prevents or reduces the formation of non-microbial malodor due to adsorbed armpit or crotch area sweat on the garment. As a carrier for fabric treatment, the thiol heterocyclic deodorant may be deposited onto the garment before washing or drying the garment, or the deodorant may be deposited onto the garment before the garment is used or worn. There are liquid and granular fabric conditioning compositions and rash and/or odor eliminating compositions that are formulated to remain deposited during at least the initial period of wear or use.

Typically, such compositions contain from about 0.01% to about 20%, preferably about 0.0%, of the thiol heterocyclic compound of the invention.
Contains 1 to about 10%.

D. Sanitary products and diapers Another aspect of the present invention relates to a composition for suppressing non-microbial malodors, comprising an adsorption base material carrier for sanitary products or diapers and the deodorizer of the present invention. As used herein, "adsorbent substrate carrier" refers to an adsorbent layer or core of material containing wood bulb fibers, cotton fibers, polyester fibers, or other liquid or solid adsorbent materials. Deodorizing compositions containing the deodorizing agent of the present invention for use in suppressing urine-based and menstrual fluid-based malodors include, but are not limited to, sanitary products such as sanitary napkins and panty liners, and diapers for infants and adults. . Another aspect of the present invention provides deodorizers and deodorizing/preservative compositions for use in toilet bowls, cosmetic utensils, sanitary products, and bedding, including the deodorants and fragrances or antibacterial agents of the present invention.

E. Method The present invention provides a method of topically applying a safe and effective amount of one or more thiol heterocyclic compositions of the present invention to areas of the skin that are subject to secretion of both apocrine and ephrine sweat, namely the axillary and groin regions of the body. Preferably, a method of suppressing or inhibiting human sweat malodor is also provided.

Methods of using the compositions of the present invention to control non-microbial malodors include topical application of the compositions of the present invention, wherein the compositions are applied in an amount of from about 0.002 to about 4.0 mg, preferably from about 0.01 to about 4.0 mg.
Preferably, the application is such that about 1.0 mg of deodorant is applied per cd of skin.

Additionally, the present invention provides a method for controlling non-microbial malodor in clothing and fabrics by depositing a safe and effective amount of the thiol heterocyclic agent of the present invention into the clothing or fabric. Preferably, the deodorizing composition is applied to the garment in areas that, when worn, typically come into contact with both the ephrine and apocrine glands, particularly the axillary and crotch areas. Preferably,
From about 0.002 to about 4.0 mg, preferably from about 0.01 to about 1.0 mg, of the thiol heterocyclic deodorant is deposited per cd of clothing or fabric.

The invention also provides a method of contacting an article of clothing or fabric with an aqueous detergent solution containing from 0.1 to about 2% by weight of the detergent composition of the invention. Fabrics to be laundered are agitated in these solutions, preferably in automatic washing machines, to provide cleaning, soil removal, fabric care benefits, and odor control.

The composition can also be applied to the article by tamping the garment or fabric in an automatic washer/dryer.

The present invention also provides a method for suppressing malodor, which involves contacting or depositing the thiol heterocyclic deodorant of the present invention on sanitary products that come into contact with urine, feces, and/or menstrual fluid. A preferred method further involves contacting or depositing a deodorant onto the sanitary product containing the adsorbent substrate carrier.

The following non-limiting examples describe compositions of the invention.

Examples 1-24 Gel-type solid deodorizing compositions are prepared from the ingredients shown in Tables 1-4 below.

sword · · · · · . --- towards ・ ・
・ ・ −・ −−〜Ma1 ・ ・ ・
g ・ ・ --~n1 ・ ・ huge ・ ・
・ −−〜field ・ −・ ・ ・ ・ −−〜 -8 kites 12 , \ total 11
, O[F]-t-% to the bottle (g) size C'1 to H-Shigeichi = 1 ・ ・ ・ ・ ・ °゛°°゛脩 Ko Koi! Meeting mouth also heart-ya f L rrr f +10
・\”Job 11. Hehehe (to) size Hehehe, ＼U-ku rehehehe~-go・ ・ ・ ・ ・
;-1~ The acid compound consisting of the above is manufactured by mixing various components. The mixture is heated to about 88°C and stirred. The mixture is then poured into molds and rapidly solidified upon cooling.

Examples 25-36 Kel-type solid deodorizing compositions are prepared from the ingredients shown in Tables 5 and 6 below.

The composition consisting of the above composition is produced by mixing the various components. The mixture is heated to about 88°C and stirred. The mixture is then poured into stick molds and rapidly solidified on cooling.

Example 37 The following liquid deodorizers are manufactured.

Ingredients % (weight) 2-Thiohistidine 1.0 Triclosan 0.5 Water
92.5 ethanol 5.0 EDTA
1.0 Mix the above acids and place in a conventional pump spray equipment. The composition can be sprayed directly onto the axillary and crotch areas of the skin or onto the axillary and crotch areas of clothing.

Example 38 A deodorizing composition in aerosol form according to the invention is prepared from the following components: Component % (weight ff
1) 2-Thiohistidine 1.0 Triclosan 0.4 Ethanol 14.8 Propylene glycol 14,8 Isobutane (propellant) 70.0 The aerosol deodorizer consisting of the above is a mixture of 2-thiohistidine, triclosan, ethanol and propylene glycol. and placing the mixture in a conventional aerosol can. The propellant is then added under pressure and the can sealed.

Example 39 A liquid deodorizing composition for topical application to the skin from a pump spray bottle is prepared from the following ingredients: Ingredients
% (weight) glycerol
49.8 ethanol
49.8 Triclosan
0,34.5-Diamino-6-hydroxy-2-mercaptopyrimidine 0.1 Liquid deodorizer is prepared by mixing the above components and adjusting the mixture to pH 9 with NaOH.
, 0 and placing the mixture in a conventional pump spray bottle.

Example 40 A liquid deodorizing composition for topical application to the skin from a roll-on bottle is prepared from the following ingredients: Ingredients
% (weight → glycerol
49.8 ethanol
49.8 Triclosan
0.32-Thiohistidine
0.1 liquid deodorizer is prepared by mixing the above ingredients, adjusting the mixture to pH 9.0 with NaOH, and placing the mixture in a conventional roll-on bottle.

Example 41 The purpose of this example is to illustrate the effectiveness of the present invention in neutralizing and inhibiting non-microbial malodors.

Various thiol heterocyclic deodorants were added to concentrated artificial sweat in an in vitro study. Sterile concentrated artificial sweat was prepared by containing an aqueous solution of pyridoxal phosphate and an aqueous solution containing natural apocrine gland secretions. Concentrated artificial sweat for each test was prepared according to the following procedure, however, it was not necessary to prepare it simultaneously for each test deodorant.

The aqueous pyridoxal phosphate solution contained 12.4 mg of pyridoxal phosphate per 10 ml of 20IIIM tris(hydroxymethyl)aminomethane, and was adjusted to pH 7 with HCI.
It was adjusted to 5.

Natural human apocrine gland secretions were collected by firmly rolling the ball of a conventional deodorant roll-on bottle against the skin in the axillary region for at least six known malodorous substrate producers for 1 minute each. The roll-on bottles were each filled with HCI prior to collection of apocrine secretions.
It contained 10 ml of 20d) lis(hydroxymethyl)aminomethane adjusted to pH 7.5. Then mix together each bottle of avocrine gland secretion solution,
It was sterilized by filtration through a 0.22μ acetate membrane and then heat treated at 80°C for 30 minutes. The apocrine gland secretions were sterilized to eliminate the development of non-microbial odors during the test.

The artificial sweat composition was prepared by mixing 1 part by volume of pyridoxal phosphate solution with 5 parts by volume of apocrine gland secretion-containing solution under sterile conditions.

The thiol heterocyclic deodorizer was applied under sterile conditions with 0.0% thiol heterocyclic deodorant. Add to 6.0 ml of artificial sweat composition sample at 7mM concentration and
Incubated for 8 hours.

At the end of the incubation period, the sweat samples were sensory evaluated by sniffing the contents and comparing the odor with a control sample of the above sex (the control sample was incubated for the same period and under the same conditions as the deodorant-containing sample). (However, it does not contain a thiol heterocyclic deodorant). A strong malodor was observed at the end of the incubation period for the control samples.

The following thiol heterocyclic compounds were tested at a concentration of 0.71 in artificial sweat (corresponding approximate g loading is given in parentheses): 2,4-diamino-6-mercaptopyridine (0,7 mg); 2-thiouracil (0.6 mg
) ;4. 5-diamino-5-hydroxy-2-mercaptopyrimidine (o, 8■), 2-mercaptobenzoxazole (o, 8■); 2-mercaptopyridine (0,6mg); and L-thiohistidine (0,9
111g). In each case, the thiol heterocyclic compound substantially reduced the production of non-microbial malodors compared to the matched control sample.

Malodor from a sweat sample prepared substantially as in the control sample above was found to be 0.0% in the sweat sample after ink heating. 7mM concentration 4. 5-diamino-6-
A significant reduction, ie, neutralization, was also observed with the addition of hydroxy-2-mercaptopyridine.

Example 42 A granular detergent composition for household laundry is as follows: Ingredients
Amount (%) Sodium C14-C15 alkyl sulfate
J3,3C13 linear alkylbenzene sulfonate sodium 5.7CI2
- C137 alkyl polyethoxylate (6,5)
1.0 Sodium toluenesulfonate
1.0*TMS/TDS
Sodium salt, TMS: TDS heavy'ftjt8G/1
4 25. ON-Hydroxyethylethylenediamine sodium triacetate 2.0 Sodium polyacrylate (average H1 approximately 5000) 2
．． 0 Sodium carbonate
20.3 Sodium silicate
5.8 polyethylene glycol (average H1 approximately 8000) 1
．． 02-Thiohistidine
i.

Sodium sulfate, water and others”
29.1100.0 *TMS/TDS - Mixture of tartaric acid monosuccinate and tartaric acid disuccinate in the sodium salt form at a weight ratio of TMS to TDS of 85/15 Loga Ingredients including flavoring agent, buffering agent, coloring agent, opacifying agent, etc. Excess water (approximately 40% total) is added together with continuous mixing to form an aqueous slurry and then spray dried to form the composition. Ergothioneine or other thiol heterocycles useful in the compositions of the invention may replace the thiol heterocycles in the compositions.

Example 43 A liquid detergent composition for household laundry is as follows: Ingredients
Amount (%) C14-C15 alkyl polyethoxy (
2,5) Potassium sulfate 8.3CI2-014 alkyldimethylamine oxide 3.3
Potassium toluenesulfonate
5.0 monoethanolamine
2,3TMS/Tf)S triethanolamine salt, 85/15 TMS:TDS
15.01.2-dihydroxy-3,5
- Disulfobenzene potassium salt 1.5 potassium polyacrylate (average M, W, about 9000)
1.52-Thiohistidine
i.

Water and other *82.1 100.0 1 Ingredients, including fragrances, buffers, colorants, opacifiers, etc., are added together in continuous mixing to form the composition. Ergothioneine or other thiol heterocycles useful in the compositions of the invention may replace the thiol heterocycles in the compositions.

Example 44 Fabric conditioning agent ingredients
Amount (%) Ditallow dimethylammonium chloride (DT
DMAC) 3.7 methyl to 1-tallow amidoethyl 2-tallow imidazoline 3,7
2.2--Dipyridal disulfide
3.0 Water and Others 1 F89.6 100.0 1 Contains Fragrances, Buffers, Colorants, Opacifiers, etc. Example 45 Another granular detergent composition of the present invention includes the following ingredients:
minutes
% (wt) 12.3 Sodium linear alkylbenzene sulfonate 15.8 Sodium C14-C15 alkyl sulfate 6.
8012-013 Alcohol Ethoxylate (EO6)
0.5 Sodium tripolyphosphate 6.8 Sodium birophosphate
13.1 Sodium pyrophosphate acid
12.4 Sodium silicate 1 function (NaO/5jO2 ratio 1..6)
7.6 Polyethylene glycol 8000
0.8 Sodium polyacrylate (M Niray 4500)
3.4 Protease enzyme *1.8 Sodium perborate tetrahydrate
1.9 Sodium sulfate
14.44.5-Diamino-6-hydroxy-2-mercaptopyrimidine 0.05
Remainder (including water, brightener, fragrance, anti-foaming agent)
14.85100.0 T) H9,2 of a 1% aqueous solution at 20° C. Anson units/g of an aqueous clarification mix of the reported detergent composition is prepared and spray dried with the exception of sodium pyrophosphate acid, Enzymes and fragrances are mixed so that they contain the indicated levels of the ingredients.

Example 46 Another granular detergent composition for household laundry is as follows: Ingredients
Amount (%) Sodium C14-C15 alkyl sulfate
13,3C13 linear alkylbenzene sulfonate sodium 5.7C1
2-C13 alkyl polyethoxylate (6,5)
1.0 Sodium toluenesulfonate
1.0 T wings/TDS sodium salt, TMS:Tlβ weight ratio 1116/14
25. ON-Hydroxyethylethylenediamine sodium triacetate 2.0 Sodium polyacrylate (Average M value approx. 5000) 2.0
sodium carbonate
20.3 Sodium silicate
5.8 polyethylene glycol (average M, W, about 8000>
1.02.4-Diamino-6-mercaptopyrimidine
0.05 sodium sulfate, water and others” 22.85100.0 *TMS/TDS - Mixture of tartaric acid monosuccinate and tartaric acid disuccinate in sodium salt form in weight ratio of TMS to TDS 85/15 Loga flavoring agent, buffering agent The ingredients, including colorants, opacifying agents, etc., are added together with a sufficient excess of water (approximately 40% total) with continuous mixing to form an aqueous slurry, which is then spray dried to form the composition.

Example 47 Another liquid detergent composition for household laundry has the following ingredients:
Amount (%) C-C alkylpolyethoxy(2,5) potassium sulfate 8,3C12-C1,4 alkyldimethylamine oxide 3.3 Potassium toluenesulfonate
5.0 monoethanolamine
2.3 TMS/TDS l-liethanolamine salt, 85/15 TMS/TDS
15.01.2-dihydroxy-3,5-disulfobenzene potassium salt 1.5 Potassium polyacrylate (average M value approximately 9000) 1.5
2-Thiohistidine
0,01 water and other books
B3.09ioo.

1. Ingredients including fragrances, buffers, colorants, opacifying agents, etc. are added together in continuous mixing to form a composition.

Example 48 Fabric conditioning agent ingredients
Shinpasho and ditallow dimethylammonium chloride (D
TD)4AC)3.7methyl-1
-Tallow amidoethyl 2-Tallow imidazoline 3.
72-Mercaptopyridine
0,1 water and others
92.5 ioo.

The disclosed thiol heterocyclic compounds inhibit human perspiration as well as a variety of other malodors. Such other malodors include, but are not limited to, environmental odors and chemical odors. In addition, the disclosed thiol heterocyclic compounds can be used in a variety of porous materials including, but not limited to, plastics, wood, hair, glass, porcelain, fabrics, fibers of various compositions, foods and beverages. suppresses negative odors generated from or deposited on porous and non-porous surfaces. or by applying a thiol heterocyclic compound to these surfaces during production.As used herein, "suppressing odors, malodors, or negative odors" means
It means preventing, inhibiting or converting such odor formation.

“Negative odor or malodor” as used here is:
Refers to an undesirable odor emanating from a specific surface or product.

The inventors have discovered that the disclosed thiol heterocyclic compounds, preferably 4,5-diamino-6-hydroquine-2-mercaptopyrimidine, 2,4-diamino-6-mercaptopyrimidine, 2-thiohistidine, 2-mercaptopyrimidine, It was further determined that pyridine and 4-mercaptopyridine are highly effective in controlling malodors associated with laundry cleaning products. Although the mechanism involved in this deodorization is unknown, it is thought to be something other than interaction with the vitamin B6 reaction. Although such surprising applications are extremely useful in laundry product compositions that do not contain fragrances, it is important to note that these compositions do not contain any substitutes for them, including but not limited to solvents, enzymes, surfactants, or contaminants. This is because they often have negative odors emanating from objects. In addition to deodorizing these negative odors, thiol heterocyclic compounds enhance positive odors in laundry products such as fragrances.

The present invention further relates to compositions effective in controlling malodors associated with chemical formulations of laundry cleaning products. A laundry product composition with a negative laundry product component of about 0.00
Contains from 1 to about 20% thiol heterocycle.

The invention further relates to methods effective in controlling malodors associated with chemical formulations of laundry cleaning products. A method for controlling negative laundry product appearance includes from about 0.001 to about 20% thiol heterocycle in the laundry product composition.

Applicant's representative: Mr. Sato

Claims (1)

[Scope of Claims] 1. A deodorizing composition for suppressing bad odor caused by perspiration, which comprises: a) a safe and effective amount of a thiol heterocyclic compound; (1) the above compound contains oxygen, nitrogen, and sulfur in the ring structure; a heterocyclic structure having at least one selected heteroatom, preferably from 1 to 3 heteroatoms, preferably nitrogen, preferably the nitrogen heteroatom is bonded directly to the oxygen atom to form the N-oxide; (2) the heterocyclic structure has at least one thiol substituent attached to a carbon atom of the heterocycle; and (3) preferably the ring structure is unsubstituted or unsubstituted other than the thiol substituent. and b) a topical carrier; and is worn on or near the skin; A composition characterized in that it is suitable for application to clothing. 2. The deodorizing composition for suppressing bad odor caused by perspiration according to claim 1, further comprising an antibacterial deodorizing agent. 3. The thiol heterocyclic compound is selected from heterocyclic compounds having a thiol-substituted heterocycle with delocalized electronic structure, in which case at least one thiol substituent is: a) a double bond to the heterocycle nitrogen or sulfur atom; b) bonded to a carbon atom of the heterocycle that is bonded by a conjugated double bond to the nitrogen or sulfur atom of the heterocycle; or c) bonded to an oxygen atom of the heterocycle. The deodorizing composition for suppressing bad odor from perspiration according to claim 1 or 2, wherein the deodorizing composition is bonded to a heterocyclic carbon atom that is double bonded to a heterocyclic carbon atom adjacent to a heterocyclic oxygen atom. 4. The thiol heterocyclic compound is thiophene, furan, pyran, isobenzofuran, chromene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, isoindole, indole, purine, quinolidine, isoquinoline, quinoline,
The deodorizing composition for suppressing perspiration malodor according to claim 3, selected from thiol derivatives of phthalazine, naphthyridine, quinoxaline, quinozoline, cinnoline, pteridine, oxazoline, isothiazole, oxazole and isoxazole, preferably pyridine, pyrimidine, quinoline and imidazole. thing. 5. The thiol heterocyclic compound is 5,6-diamino-2-
Thiouracil, 4,5-diamino-6-hydroxy-2
-Mercaptopyrimidine, 2-thiouracil, 2,4-
Diamino-6-mercaptopyrimidine hemisulfate, ergothioneine, 2-thiohistidine, 2-mercaptopyridine, 4-mercaptopyridine, 2-mercaptobenzoxazole, 2-mercapto-6-nitrobenzothiazole, 2-thiocytosine, 6-thioxanthin ,2,
6-dimercaptopyridine, 2-mercapto-5-nitropyridine, 2-mercaptoquinoline, 2-mercapto-4-hydroxy-6,8-dichloroquinazoline, 2-
Mercaptopyrimidine, 4-mercaptoquinazoline, 2
-Phenyl-4-quinazothiol, 3-amino-6
-Methyl-4-pyridazinethiol, 5-amino-4-
Pyridazinethiol, α-tocopherthiol, 2-amino-6,7-dimethyl-4-pteridinethiol, 4
-Mercaptopteridine, 2-mercapto-4-hydroxypteridine and 2,4-diamino-6-phenyl-
7-pteridinethiol, preferably 2-mercaptopyridine, 4-mercaptopyridine, 2,4-diamino-
The deodorizing composition for suppressing bad odor from perspiration according to claim 4, which is selected from 6-mercaptopyrimidine, 2-thiohistidine, and ergothioneine. 6.a) at least one thiol substituent having a heterocyclic structure having at least one heteroatom selected from oxygen, nitrogen, and sulfur in the ring structure, and the heterocyclic structure is bonded to a carbon atom of the heterocycle and b) a carrier for laundry products. 7. The thiol heterocyclic compound is pyridine, pyrimidine,
7. Deodorizing composition according to claim 6, selected from thiol derivatives of quinoline and imidazole. 8, a) at least one thiol substitution having a heterocyclic structure having at least one heteroatom selected from oxygen, nitrogen, and sulfur in the ring structure, and the heterocyclic structure is bonded to a carbon atom of the heterocycle; A deodorizing composition comprising: a safe and effective amount of a thiol heterocyclic compound having a group; and b) a carrier for fabric treatment. 9. A method for suppressing malodor from clothing, comprising depositing a safe and effective amount of the composition according to claim 7 or 8 on the clothing.