WO1993017661A1

WO1993017661A1 - Cosmetic compositions free of malodors

Info

Publication number: WO1993017661A1
Application number: PCT/US1993/001791
Authority: WO
Inventors: Diane Lynn Furio; Paul Robert Tanner; John Paul Luebbe
Original assignee: The Procter & Gamble Company
Priority date: 1992-03-11
Filing date: 1993-03-01
Publication date: 1993-09-16
Also published as: MX9301359A

Abstract

Cosmetic compositions containing zeolitic materials to reduce malodors associated with the materials in the cosmetic base of the composition. The zeolitic materials include intermediate zeolites, mordenites, beta zeolites, and combinations thereof. Also disclosed herein is the process for making the cosmetic compositions.

Description

COSMETIC COMPOSITIONS FREE OF MALODORS

TECHNICAL FIELD

The present invention relates to cosmetic compositions essentially free of the malodors associated with the raw materials comprising an odoriferous cosmetic base.

BACKGROUND OF THE INVENTION

Cosmetic compositions are made from a variety of cosmetic raw materials. These materials include fatty materials, waxes, emollients, humectants, moisturizers, e ulsifiers, colorants, perfumes, and other ingredients typically described in standard references.

Typical cosmetic compositions are expected to deliver cosmetic benefits with acceptable odor. However, many of the materials used in a cosmetic base either have an inherient odor, acquire malodors during processing and storage due to degradation, or have impurities contained in them which are malodorous.

Various odor-reducing agents have been disclosed in the literature. For example, certain zeolitic materials are known for use in sorbent articles, such as disposable diapers and cata enials, to effectively reduce many odors associated with body fluids.

It has now been determined that certain zeolitic materials are effective in controlling the malodors associated with cosmetic raw materials comprising the cosmetic base of the present invention. The odor-reducing zeolitic materials useful in the present invention are selected from the group consisting of "intermediate ratio" (Si0₂/Al₂0₃) Y zeolites, ordenites, large-pore beta zeolites, and mixtures thereof. These zeolitic materials are compatible with various cosmetic raw materials used in the cosmetic arts. The present invention is, therefore, particularly useful in unscented cosmetics, but is also useful for improving the fragrance quality of scented cosmetics.

BACKGROUND ART

The literature in the art contains a considerable number of references relating to odor reduction. The following are illustrati*' U.S. Pat. 4.362.715, Strianse et al . (12/7/82) teaches the use of zeolite material to provide desirable rheology to cosmetic compositions such as astringent creams or lotions. The zeolite material also provides cosmetic benefits due to the aluminum cations interacting with the skin.

U.S. Serial No. 07/714111. Furio et al . (filed 6/11/91) teaches using intermediate ratio Y zeolites to reduce odors, particularly ammonia-type odors, in disposable articles such as diapers. U.S. Serial No. , Fieldstad et al . (concurrently filed with the present application), teaches syndet compositions containing intermediate ratio Y zeolites to remove compositional malodors.

U.S. Pat. 4,855.154, Gioffre et al . (issued 8/8/89), teaches deodorization of marine or fish oils using molecular sieves to sorb organic amines and other odor producing molecular species, such as aldehydes and ketones.

U.S. Pat. 4.961.881. Ou, (issued 10/9/90), teaches the separation of polyunsaturated triglycerides by sorption using copper-exchanged alumino-silicates.

U.S. Pat. 4.385.632 S. 0. Odelhδg, (issued 5/31/83), teaches using copper salts, such as copper chloride, to impede bacterial growth in sorbent products reducing odors, particularly ammonia. Japanese J63224734-A (88.09.19) Priority 87JP-058738 (87.03.16) J63224734 ASK KK relates to a paper comprising a powder or fiber obtained by grinding sepiolite, said paper having deodorizing capacity.

Japanese J63242261-A (88.10.07) 87JP-076111 J63242261 ASK KK relates to an odor-sorbing mat with sepiolite powder, a nonwoven fabric layer, and what appears to be a sheet to which the sepiolite is attached by adhesive.

U.S. Pat. 2.690.415. F. A. Shuler (issued 9/28/54), teaches particles of odor-sorbing materials uniformly affixed at the interstices of a permeable web by adhesive to provide an odor reducing medium for, e.g., cata enials. Particulate carbon, silica gel and activated alumina are noted. Shifting/displacement of the particulates is assertively avoided and the sheet is flexible.

Japanese J54141857 (J87019865) teaches the manufacture of powder (including zeolites) sheets by laminating the powder between a first and second sheet. Powders include activated carbon, zeolite, etc. The abstract indicates use in catamenials or deodorizing materials.

The use of ABSCENTS (odor-reducing molecular sieve from Union Carbide) in diapers and catamenials is specifically noted in Union Carbide brochure (A. J. Gioffre, 1988). U.S. Pat. 4,795,482, Gioffre et al . (issued 1/3/89), and U.S. Pat. 4,826,497, Marcus et al . (issued 5/2/92), relate to ABSCENTS used as an odor-reducing agent, generally, and in sanitary products, in particular.

All documents cited in this specification are incorporated herein by reference.

SUMMARY OF THE INVENTION

The present invention relates to cosmetic compositions essentially free of raw material malodors. By cosmetic compositions, the Applicants mean any preparation of a liquid, semi-liquid, paste, powder, solid or other compositional form which when applied to the body protects the skin, improves the appearance and/or condition of the skin, and/or promotes other aesthetic or therapeutic conditions without specific medicinal effects. Such cosmetics are well-known in the art and are disclosed in various formularies, such as Harry's Cosmeticolocy,

Edited by Wilkinson and Moore, 7th Ed. 1982; herein incorporated by reference.

The cosmetic compositions of the present invention comprise a odoriferous cosmetic base, and greater than about 0.05%, preferably from about 0.05% to -.bout 10% by weight of the cosmetic composition, of an odor-reducing zeolitic material selected from the group consisting of intermediate ratio Si0₂/A ₂0₃ Y zeolites, ordenites, beta zeolites, and mixtures thereof.

With regard to the using the above zeolites in formulating cosmetic compositions, when minimizing abrasiveness is critical, it's suggested that the zeolitic material be substantially free of particles greater than about 30 microns, preferably greater than about 15 microns. In this context, "substantially free" means that larger particles are less than than about 5%, preferably 4%, and most preferably 3% as measured by laser light scattering. All percentages, ranges and ratios herein are by weight, except for the alumino/silica ratios which are expressed as molar ratios.

The process for making cosmetic compositions essentially free of raw material malodors is also disclosed herein. The process comprises the addition of the above disclosed zeolitic material to the liquified odoriferous cosmetic base, wherein the mixture is adequately mixed to uniformly distribute said zeolite throughout the liquified odoriferous cosmetic base.

DETAILED DESCRIPTION OF THE INVENTION The cosmetic compositions of the present invention have no perceptible malodors. This is accomplished by including specific zeolitic materials, as described more fully hereinafter. In addition to its ability to sorb malodorous materials, it has been discovered that the above mentioned zeolitic materials can also reduce residual skin irritants found in cosmetic compositions.

The following is a detailed description of cosmetic compositions of the present invention. In addition, the process for making said compositions is also disclosed. ZEOLITIC MATERIALS The cosmetic compositions of the present invention comprise an odor-reducing amount, preferably greater than about 0.05%, more preferably from about 0.05% to about 10% by weight of a zeolitic material, selected from the group consisting of intermediate ratio Si0₂/Al₂0₃ Y zeolites (herein referred to as intermediate zeolites), mordenites, beta zeolites, and mixtures thereof.

The manufacture of zeolite materials of the type used in the practice of this invention is well-known, and reference can be made to the voluminous literature for typical synthetic procedures. In general terms, traditional zeolites comprise an alumino/silicate framework, with associated cations, M, providing overall electrical neutrality. Empirically, the zeolite framework can be represented as x A10₂ . y Si0₂ and the electrical neutral zeolite as x/n M . x A10₂ . y Si0₂ . z H₂0 wherein: x and y are each integers, M is a cation and n is the charge on the cation. As noted by the empirical formula, zeolites may also comprise water of hydration (z H₂0). Reference to the literature will illustrate that M can be a wide variety of cations, e.g., Na⁺, K⁺, NH₄ ⁺, alkylammonium, heavy metals and the like. The practice of the present invention does not require any particular selection of cation; accordingly, sodium ion is con¬ venient and preferred.

The intermediate zeolites particularly useful in this invention are characterized by Si0₂/Al₂0₃ molar ratios of from about about 2:1 to about 50:1, preferably from about 2:1 to about 20:1, more preferably from 2:1 to about 10:1, and most preferably from about 4:1 to about 7:1. Particularly preferred for herein are ultrastable intermediate zeolites. By ultrastable, it is meant that the counter ion level, and the water of hydration value of the intermediate zeolites are lower than typical zeolites known in the art. For example, counter ion values for ultrastable zeolites in the present invention are from about 0 about 5.

Mordenites are also useable in the present invention. In the context of the present invention, mordenites are to be considered zeolitic materials having a needle-like structure, naturally found or a synthetic analog. The mordenites are of the formula Si0₂/Al_:0₃ wherein the ratio of Si0₂/Al₂0₃ is from about 12:1 to about 35:1, preferably from about 12:1 to about 20:1. Its surface area is from about 400 m^/ to about 550 m^/g. Examples of mordenites useful herein include CP500-11, CP511-13,CP504-20, CBV10A, CBV20A, CBV30A, and mixtures thereof.

Finally, the beta zeolites disclosed for use in the present invention have a Si0₂/Al₂0₃ ratios from about 10:1 to about 75:1, preferably from about 10:1 to about 50:1. The surface area of said particles are from about 700 m²/g to about 800 m²/g. They are also distinguished from the intermediate zeolites previously discussed by their larger pore size. The pore size of the beta zeolites are known to be greater than the intermediate zeolites since its aluminosilicate rings typically have 12 members whereas the rings in the intermediate zeolites typically have no more than 10.

A wide variety of intermediate, and higher ratio ultrastable Y zeolites, suitable for use herein, are commercially available from commercial suppliers such as PQ Corporation, Mobil Corporation, and UOP. Such materials are sold under various commercial and trade names such as VALFOR CP301-68, VALFOR 300-63, VALFOR CP300-35, VALFOR CP300-51, VALFOR CP300-56, CP800 series, CBV10A-30A series, and the CBV300 to CBV780 series all from PQ Corporation.

While not intending to be limited by theory, it appears that the alumino/silicate ratios of the zeolitic materials for use in the present invention result in several advantages over the "high" zeolites. The presently disclosed zeolites have a larger surface area (700-800 m^z/g) than the high zeolites (ca. 400 m²/g). This results in more efficient odor sorption, on a wt./wt. basis; or, in the alternative, allows less zeolite to be used to reduce a given amount of odor. These zeolites have a relatively low affinity for moisture, thereby, retaining more of their odor-sorbing capacity in the presence of water. Surprisingly, these zeolites act to sorb product odors even in liquid or solid cosmetic matrices which completely encompass the zeolite molecule sieve structures. However, the zeolites disclosed for use in the present invention can be used in combination with other zeolites known in the art, such as high zeolites, to impart desirable characteristics to the cosmetic composition. For example, U.S. Pat. 4,362,715, as disclosed above, utilizes high zeolites to impart desirable rheology to the cream composition disclosed therein. Examples of high ratio zeolites useful for such secondary benefits include, for example, the well-known "molecular sieve" zeolites of the ZSM, pentasil, silicate type (generally in the 1-10 micron particle size range) available from PQ Corporation as the VALFOR 600 series, and their CBV MFI-Type zeolites and and the zeolite materials marketed under the trade name ABSCENTS by UOP, and which are typically available as a white powder in the 3-5 micron particle size range (see: ABSCENTS, A New Approach for Odor Control by A. J. Gioffre, copyright 1988 by the Union Carbide Corporation) .

The odor-reducing agent described above can be optionally combined with the other odor sorbing materials, such as "high ratio" zeolites. Such materials include, for example, The use of zeolites of the ABSCENTS type to reduce odors is fully described in U.S. Patent 4,795,482, January 3, 1989, to Gioffre and Marcus. These agents are reported by Gioffre and Marcus to be crystalline siliceous molecular sieves in which at least about 90, and preferably at least about 95, percent of the framework tetra- hedral oxide units are Si0₂ tetrahedra and which have a sorptive capacity for water at 25^*C and 4.6 of less than 10 weight percent. In the case of aluminosilicate molecular sieves, those "high ratio" zeolite odor-reducing agents have a framework Si0₂/Al₂0₃ molar ratio of from about 35 to infinity, and preferably from 200 to 500. Such siliceous molecular sieves have a pore diameter of at least 5.5 Angstroms, preferably at least 6.2 Angstroms.

In order to assist the formulator and user of this invention, (but not by way of limitation), attention is directed to the synthetic procedures described in the following reference texts, all herein incorporated by reference: ZEOLITE SYNTHESIS, ACS Symposium Series 398, Eds. M. L. Occelli and H. E. Robson (1989) pages 2-7; ZEOLITE MOLECULAR SIEVES, Structure, Chemistry and Use, by D. W. Breck, John Wiley & Sons (1974) pages 245-250, 313-314 and 348-352; MODERN APPLICATIONS OF MOLECULAR SIEVE ZEOLITES, Ph.D. Dissertation of S. M. Kuznicki, U. of Utah (1980), available from University Microfilms International, Ann Arbor, Michigan, pages 2-8. The synthesis of intermediate zeolites forms no part of the present invention since various syntheses are known in the art. The following is given simply by way of illustration, and not limitation, of a synthetic procedure. Zeolite Synthesis In general, zeolites are synthesized by hydrother al crystallization of alkaline (pH >8 and preferably higher) reactant mixtures. The synthesis can be viewed as 3 major stages with each having sub-steps: (1) combining and gelation of reactants; (2) crystallization; and (3) post-treatment. The resulting zeolite is not only a function of the reactant mixture but also is equally a function of the synthetic conditions. External factors such as temperature, pressure, time, etc. highly influence the crystalline structure.

For traditional zeolites, the reactants commonly consist of: silica source + alumina source + base + water A host of starting reactants are available; some typical silica and alumina sources are noted as follows. Silica sources include: silicates; silica sol; silicic acid; silica gels; silica glass; minerals; and other zeolites. Alumina sources include: aluminum hydroxide; aluminum salts; metal aluminates; aluminum nitrate; aluminum sulfate; pseudoboehmite; and various minerals. While different starting materials can yield different zeolites, the same zeolite can be made from different reactants. Some reactant variables influencing the structure and composition of the final zeolite are:

- the identity, ratio and order of addition of the reactants; - the strength of the base;

- the temperature (ambient to ca. 100'C);

- mechanical agitation such as stirring; and

- the gelation time (1 hour to days).

Once the desired gelation is achieved, the gel is transferred to a teflon or stainless steel container and placed in an autoclave. Crystal formation begins as the gel is subjected to constant or variable temperature at autogeneous pressure for an indefinite time. There are basically 3 recognized phases during transformation of the gel to crystals. The phases are (1) induction or nucleation (first crystal appears); (2) crystal growth; and (3) phase transformation. Some factors influencing the rate at which crystals form and grow are the temperature, pH, addition of seed crystals or tempiating materials for structure directing, stirring and centrifugation. After phase transformation, the slurry is removed from the autoclave and filtered. The crystals are washed and dried at ca.

100'C. Further modifications are possible if so desired. Post-Synthesis Modifications

Some post-synthesis modifications provide other traditional zeolites. For instance, counter ions can be exchanged such as: Na-zeolite + NH₄C1 - NH₄-zeolite or

Na-zeolite + HC1 - H-zeolite imparting unique adsorptive forces and modifying the pore size of, for example, an A, X or Y zeolite. Additionally, stabilization of traditional zeolites is possible. For example, a typical method of synthesizing an ultrastable zeolite Y (USY) such as "VALFOR CP300-56" is as follows: NaY + NH₄+ or NH+ exchange - NH₄NaY + calcine (650-800'C) → USY Synthesis of Stabilized Zeolites

Several post-synthesis modification methods exist for making stabilized zeolites. The methods include (1) pore modification; (2) surface modification; and (3) structural change. The first two methods consist of adsorbing species by chemical vapor deposition inside or on the zeolite. Pore modifiers such as SiH₄ and BH₃ and surface modifiers such as Si(0CH₄)₄, SiCl₄, TiCl₄ and SeCl₄ have been used to impart new unique properties to the zeolite. The most frequently used structural change method is to remove alumina from the main framework (i.e., de-alu inate) . De-alumination can be performed by one of several routes such as (1) acid leaching; 2) steam (700-900'C); or (3) treatment with SiCl₄ at cold temperatures. An example of de-alumination is: Zeolite Y + H₄EDTA - de-alu inated Zeolite Y The following references, incorporated by reference herein, further illustrate the synthesis of intermediate zeolites of the type employed herein: Lok, B. M., Cannan, T. R., and Messina, C. A., "The Role of Organic Molecules in Molecular Sieve Synthesis" Zeolites 3, 282-291 (1983); Barrer, R. M. "Zeolites and Their Synthesis" Zeolites I , 130-140 (1981); ZEOLITES FOR THE NINETIES, Proceedings of the 8th International Zeolite Conference, Eds. P. A. Jacobs and R. A. van Santen (1989) pages 119-372; and MOLECULAR SIEVES, Adv. Chem. Ser. 1_21_, Eds. W. M. Meier and J. B. Uytterhoeven (1973). In general, these molecular sieve odor-reducing agents appear to function by entrapping by chemical adsorption odoriferous substances within their molecular lattice structures. Whatever their mode of action, these odor-reducing agents can be characterized by their physical parameters, as follows. Preferably the sorption capacity for water vapor at 25'C and a water vapor pressure (p/p₀) of 4.6 is less than 6 Weight percent. As stated by Gioffre and Marcus, the efficacy of these molecular sieves is not dependent on the presence of the water of hydration in the internal cavities of the microporous structure as a result of their hydrothermal formation. In fact, at least a major proportion, usually substantially all, of this original water of hydration is removed in the process of removing any pore-blocking te plating agent which may be present in the adsorbent. Calcina- tion effectively removes any organic moieties. Also, water washing, leaching or washing with a caustic or dilute mineral acid solution is advantageously utilized to remove extraneous synthesis reactants from the pore system. Lowering of the alkali metal content, particularly the nonzeolitic, i.e., occluded alkali metal compounds can also be beneficial. These procedures also serve to remove the original water of hydration.

As further disclosed by Gioffre and Marcus, such siliceous molecular sieves include the microporous crystalline aluminosili- cates, i.e., the zeolitic molecular sieves as well as the so- called silica poly orphs. With respect to the latter composi¬ tions, their crystal lattices are ideally formed entirely of Si0₂ tetrahedral units, but the as-synthesized forms commonly ^'contain at least trace amounts of aluminum derived from aluminum impuri¬ ties in the synthesis reagents. The aluminosil icate molecular sieves comprise the large class of well-known crystalline zeolites. These high-silica molecular sieves are either commer¬ cially available or are prepared by methods well-known in the art, involving direct hydrothermal synthesis or involving certain types of crystal lattice dealuminations. A comprehensive review article by E. M. Flanigen concerning both "high" Si/Al zeolites and silica molecular sieves is published in "Proc. 5th Int. Conf. Zeolites, Naples, 1980", L. V. C. Rees, ed., Heyden, London, pp. 760-780. It is to be understood that all such materials are referred to herein simply as "zeolites", for convenience.

Optional Adjunct Odor-Control! inq Materials The cosmetic compositions of the present invention can also contain an effective, i.e., odor-reducing, amount of various additional non-zeolitic odor-reducing materials to further expand their capacity for reducing odors, as well as the range of odor types being controlled. Other sorbents include, for example, cetyl pyrdinium chloride, zinc chloride, EDTA, etidronate, BHT, and the like.

ODORIFEROUS COSMETIC BASE

The odoriferous cosmetic base makes up the bulk of the compositions disclosed herein; the level being the difference between 100% and the level of zeolitic material being used. The odoriferous cosmetic base disclosed herein utilizes cosmetic raw materials that are well-known in the cosmetic arts, and reference can be made to the various patents mentioned herein and to the general cosmetic products patent literature and trade catalogues for a description of these raw materials. While the cosmetic raw materials comprising the odoriferous cosmetic base are well-known, the present invention resides in the novel use of specific zeolitic materials to suppress the cosmetic raw material's malodors.

As previously mentioned many of the cosmetic raw materials exhibit malodors which then are associated with the cosmetic compositions they are used in. For example, castor wax, and various fatty alcohols are known to have distinctive malodors. Although not wishing to be bound by theory, it's thought that some of the malodors associated with the cosmetic raw materials used in the present invention are a result of the degradation of said materials; for example stearyl alcohol is known to degrade into pungent materials. This degradation process may be exacerbated during processing when the materials are heated to high temperatures. Many of the types of cosmetic compositions encompassed within the meaning of the present invention are well documented in the art. In fact, the art of making cosmetic compositions dates back to great Egyptian dynasties of thousands of years ago. In addition to the specific zeolitic material, the odoriferous cosmetic base disclosed herein typically comprises cosmetic raw materials such as emollients, emulsifiers, cosmetic powders, waxes, colorants, humectants, moisturizers, suspending agents, oily materials, water, alcohol, viscosity modifiers, antimicrobials, preservatives, astringent materials, antiperspirant actives, and other conventional cosmetic materials. For example, many cosmetics compositions often contain oily materials such as branched chain organic compounds. These materials closely resemble the naturally occurring oils or lipids found on the skin. These branched compounds, particularly branched chain esters, typically contain more than about 6 carbon atoms and include aliphatic compounds such as 2- ethylhexyl palmitate. Cosmetic compositions containing such materials include lipsticks, eye products, and various barrier creams and lotions.

In addition to the above oily materials, many cosmetics compositions contain emollients. Emollients are considered any material which is applied to the skin to relieve dryness. deNavarre, The Chemistry and Manufacture of Cosmetics. Vol. Ill 2d. Ed. 1975. For many years, emollients were oily materials which served to replace the natural surface lipids of the skin. Id. The best known of the typical emollients used in the art is glycerine. Other emollients which are often used by the artisan to formulate cosmetic compositions include those disclosed in Fox, Antiperspirant & Deodorant Review and Update, 100 Cosmetics & Toiletries, 1985; incorporated herein by reference. Among these are silicones, fatty esters, propoxylated alcohols, and hydrocarbon oils.

A necessary component found in most cosmetic compositions is an emulsifier, or coupling agent. These materials function to create an interface between immiscible components, for example aqueous based materials and oil based materials, typically used in cosmetic composition. Absent said emulsifiers, the cosmetics would not exist in a single homogeneous phase for any length of time. Emulsifiers can be finely divided powders, or molecular species containing both hydrophilic and hydrophobic entities. Of the later emulsifier, literally thousands of these are available, and are selected on the basis of, for example color, odor, taste, price, and toxicity. Said emulsifiers, known as surfactants, include those shown in the above mentioned article by Fox.

As mentioned previously, many other components are known for use in cosmetics for both aesthetics, skin therapy or both. Many of these materials are selected based on the function they serve, as well as the form the cosmetic composition may take. For example, a moisturizing cream is likely to contain more emollients^', moisturizers, and humectants than an antiperspirant stick. Therefore, for purposes of efficiency, the Applicants will herein disclose various forms the cosmetic compositions of the present invention can take and disclose therein the typical components used therein. Examples of components incorporated within the present invention include antiperspirant and deodorant solids, antiperspirant and deodorant liquids, lotions, creams, and sprays, cosmetic solids, lotions, creams, and liquids. Preferred compositions are deodorant or antiperspirant compositions in solid form.

Solid Cosmetic Sticks

The three main forms of solid cosmetic sticks are compressed powder sticks, gel sticks, and wax sticks. The differences between these sticks is within the skill of an artisan and is well known in the art. Cosmetic sticks are disclosed in detail in U.S. Pat. 4,944,937 issued July 31, 1990; U.S. Pat. 4,919,934, issued April 24, 1990; and U.S. Pat. 4,822,602 issued April 18, 1989; all herein incorporated by reference. In the present invention, the solid stick cosmetic compositions are preferably gel and wax sticks, most preferably wax sticks.

Compressed powder or suspensoid sticks are made by isostatic compaction of selected powders and granulation containing binders such as microcrystall ine cellulose. Various other ingredients, such as selected emollients can be introduced to facilitate good skin glide.

Gel based sticks of the present invention comprise a liquid material selected for the desirable properties they impart. The liquid material is from about 60% to about 99% by weight of the composition. The liquid material useful herein includes those known in the art for making gel sticks. These include, for example, water, lower monohydric alcohols, polyhydric alcohols, and mixtures.

In addition to the liquid material, the present gel stick uses solidifying agents to impart a stable physical structure to the gel stick. The solidifying agents are selected on the basis of the desired hardness of the final composition, the liquid base materials, and additional components which may be used. The solidifying agent of the present invention is from about 1% to about 30% by weight of the composition. Solidifying agents useful herein includes those known in the art for making gel sticks. These include, for example, fatty acid soaps; amides of higher fatty acids; higher fatty acid amides of alkylolamides; dibenzaldehyde- onosorbitol acetals; alkali metal and alkaline earth metal salts of the acetates, propionates, and lactates, waxes, and mixtures thereof.

Wax based sticks of the present invention comprise a liquid material selected for the desirable properties they impart. The liquid material is about 30% to about 90% by weight of the composition. Liquid materials useful herein include those known in the art for making wax sticks. These include, for example, silicones, hydrocarbon oils, esters, propoxylated and/or ethoxylated alcohols, and mixtures thereof.

In addition to the liquid material, the present wax sticks uses solidifying agents to impart a stable physical structure to the said stick. The solidifying agents are selected on the basis of the desired hardness of the final composition, the liquid base materials, and additional components which may be used. the solidifying agent of the present invention is from about 1% to about 30% by weight of the composition. Solidifying agents useful herein includes those known in the art for making wax sticks. These include, for example, fatty alcohols, fatty acids, fatty ester, triglycerides, and waxes having melting points from about 65'C to about llO'-C. Said waxes are selected from the group consisting of beeswax, spermaceti, carnauba, baysberry, candelilla, montan, ozokerite, ceresin, paraffin, castor waxes, synthetic waxes such as Fisher-Tropsch waxes, microcrystall ine wax, and mixtures thereof.

In addition to the components above, both wax and gel sticks can contain a variety of other cosmetic ingredients as previously discussed above. For example, antiperspirants and deodorants are two of the more common cosmetic sticks made. Antiperspirants are typically produced as wax type sticks since the astringent metal actives such as aluminum chlorohydrate are more pH compatible in these waxy matrices. On the other hand, deodorant actives, such as antimicrobial compounds like triclosan, form stable solid compositions in gel matrices. Antiperspirant and deodorant sticks of these types are described in U.S. Patents 4,725,432;

4,743,444; 4,781,917; 4,816,261; 4,822,603; 4,985,238; and 5,019,375 ;all herein incorporated by reference.

One of the preferred compositions of the present invention is a cosmetic antiperspirant wax stick, particularly one comprising: a. from about 0.05% to about 10% intermediate ratio Si0₂/Al₂0₃ ultrastable Y zeolite; b. from about 30% to about 90% of a liquid material; c. from about 10% to about 30% of a solidifying agent; and d. from about 5% to about 50% of an antiperspirant active. Examples of antiperspirant and deodorant cosmetic stick compositions follow below: Example 1: Antiperspirant Solid Stick

Component Weight %

Cyclomethicone D-5¹ 38.81

Light Mineral Oil² 5.00

Phenyl Trimethicone³ 5.00 Stearyl Alcohol 14.50

Hydrogenated Castor Oil 4.00

Behenyl Alcohol 0.09

Talc 4.10

Zeolite⁵ 2.00 Aluminum Zirconium 26.00 Trichlorohydrex Gly⁶

Fumed Silica⁷ 0.50 inn no ¹ A cyclic polydimethyl siioxane supplied by General Electric Silicones

² Benol White Mineral Oil supplied by Witco Chemical Corporation

³ Dow Corning 556 Fluid supplied by Dow Corning

Castorwax MP80 supplied by NL Industries

⁵ VALFOR CP300-51, an intermediate zeolite available from PQ Corporation

⁶ Reheis AZZ902M supplied by Reheis Chemical Company

7 Cal-O-Sil HS-5 supplied by Cabot Corporation

All of the ingredients are combined and heated to 80'C with agitation. The batch is then cooled to about 52'C and poured into canisters.

Example 2: Deodorant Gel Stick

Component Weight %

Dipropylene Glycol 55.0

Propylene Glycol 21.7 Water 10.0

PPG-3 Myristyl Ether 5.0

Sodium Stearate 7.0

Triclosan 0.3

Zeolite* 1.0 100.00 I CBV10A, a ordenite available from PQ Corporation

All materials except water are combined and heated to 90°C with agitation. The water is then added and the batch is cooled and poured into canisters. Cosmetics Creams

Cosmetic creams, for example skin creams, typically signify a solid or semi-solid emulsion. Said emulsions typically are either oil-in-water or water-in-oil emulsions. The selection of cosmetic raw materials useful in such creams is extensive, with the selection based in part upon the desired purposes for said cream, for example, moisturizing and conditioning skin, imparting color or shades, delivering protectants such as sunscreens, deodorants, and antiperspirants, and numerous other functions. Regardless of their function, most creams contain a fair amount of lipid materials. For example U.S. Patent 4, 976,953,

Orr et al . , issued 12/11/90, and incorporated herein by reference, discloses skin conditioning cream compositions comprising from about 1% to about 60% propoxylated glycerol derivatives, 5% to 10% emollients, a suitable emulsifier, and the balance water. U.S. 4,853,214, Orr et al . , issued 8/1/89 and U.S.

4,840,789, Orr, issued 6/20/89, both herein incorporated by reference, disclose antiperspirant cream compositions comprising among other ingredients, 0.1% to about 60% of non-volatile emollients.

Below is an example of a cosmetic cream of the present invention. Example 3: Skin Cream

Component Weight % Oil Phase: Mineral Oil 8.0

Lanolin 2.0

Dimethicone 350 csk 1.0

Stearic acid 5.0

Glyceryl Monostearate 5.0 Cetyl Pal itate 5.0

Cetyl Alcohol 2.9

Zeolite_! 0.1

Water Phase: Triethanolamine 1.0 Propylene glycol 5.0

Water 64.9

Preservatives 0.1 ₁CBV400, an intermediate zeolite available from PQ Corporation

The oil phase and water phase are separately heated to 80°C with agitation. The water phase is then added to oil phase with good agitation, and the crean is then cooled to room temperature. Cosmetic Lotions

Cosmetic lotions typically signify liquids which can be readily spread over the surface of the skin. Viscosities are significantly lower than creams disclosed above. Lotions can be comprised of all miscible components, like alcohol and water after shave lotions, or at least in part a non-solubilized component which is suspended in the liquid carrier of said lotion. For example, U.S. Patent 4,976,953, cited above, discloses skin conditioning lotions comprising from about 1% to about 60% propoxylated glycerol derivatives, 5% to 10% emollients, and the balance water. Below is an example of a suspension type antiperspirant lotion of the present invention.

Example 4: Antiperspirant Roll-on

Component Cyclomethicone D-5

Dimethicone 50 csk¹

Polyethylene Spheres²

Quaternium-18 (Ditallow

dimethyl ammonium chloride) Hectorite³

Propylene Carbonate 0.8

Aluminum Zirconium

Trichlorohydrex Gly⁴ 20.0

Zeolite⁵ 4.0 100.00

¹ Dow Corning 200 Fluid supplied by Dow Corning

² Microthene ML-733 supplied by U.S. Industrial Chemicals ³ Bentone-38, supplied by NL Industries

⁴ Supplied by Reheis Chemical Company

⁵ CP811-25, a beta zeolite available from PQ Corporation

All of the ingredients are combined with agitation. The batch is then milled with a Tekmar mill, and poured into roll -on containers.

Lipsticks

Lipsticks are cosmetics that are molded into sticks, and are essentially dispersions of coloring matter in a base comprising a blend of oils, fats, and waxes. A greasy base is used to provide a desirable moist appearance on the lip surface. This base also provides excellent e olliency. For a more extensive discussion see Harry's Cosmeticology, Edited by Wilkinson and Moore, 7th Ed., 1982. Example 5 Component Weight %

HD Eutanol 20.00

Castor Oil 24.70

Lanolin (anhydrous) 8.00

Beeswax (bleached) 5.00 Candelilla Wax 3.00

Carnauba Wax 8.00

Ozokerite 11.00

Liquid Paraffin 13.00

Bromoacid 0.20 Pigment color 7.00

Antioxidant, perfume 0.05

Zeolite^ 0.05

100.00

ALFOR CP300-51, an intermediate zeolite available from PQ Corporation Dissolve the bromoacid in the HD-Eutanol and heat to about 80°C. Melt the remaining fatty materials, add the pigments to this solution, and add the mixture into the bromoacid/Eutanol solution above. Lower the temperature of this mixture to about 60°C, and add antioxidant and perfume. Pass the mixture through a roller mill two or three times, and remelt the solidified material. Pour the molten mixture into lipstick molds, and add color blends.

Claims

WHAT IS CLAIMED IS:

1. A cosmetic composition essentially free of raw material malodors comprising an odoriferous cosmetic base, and greater than 0.05%, preferably from 0.05% to 10% by weight of the composition of an odor-reducing zeolitic material selected from the group consisting of intermediate ratio Si0₂/Al₂0₃ Y zeolites, mordenites, beta zeolites, and mixtures thereof, preferably the intermediate ratio Si0₂/Al₂0₃ Y zeolites, and most preferably the ultrastable intermediate ratio Si0₂/Al₂0₃ Y zeolites.

2. A composition according to Claim 1 wherein the Si0₂/Al₂0₃ molar ratios of the zeolitic materials are; from 2:1 to 50:1, preferably from 2:1 to 10:1, most preferably from 4:1 to 7:1 for the intermediate zeolites; from 12:1 to 35:1, preferably from 12:1 to 20:1 for the mordenites; and from 10:1 to 75:1, preferably from 10:1 to 50:1 for the beta zeolites; wherein the the zeolitic material is in the protonic, sodium, potassium, ammonium or alkylammonium form.

3. A composition according to Claim 2 wherein the odoriferous cosmetic base contains materials selected from the group consisting of emollients, emulsifiers, cosmetic powders, waxes, colorants, humectants moisturizers, suspending agents, oily materials, water, alcohol, viscosity modifiers, antimicrobials, preservatives, astringent materials, antiperspirant actives, and mixtures thereof.

4. A cosmetic composition in the form of a solid stick essentially fre of raw material malodors comprising: a. greater than 0.05% of an odor-reducing zeolitic material selected from the group consisting of intermediate ratio Si0₂/Al₂0₃ Y zeolites, mordenites, beta zeolites, and mixtures thereof; and b. an odoriferous cosmetic base comprising from 30% to 99% of a liquid material, and from 1% to 30% of a solidifying agent.

5. An antiperspirant wax stick composition comprising: a. from 0.05% to 10% intermediate ratio Si0₂/Al₂0₃ ultrastable Y zeolite; b. from 30% to 90% of a liquid material; c. from 10% to 30% of a solidifying agent; and d. from 5% to 50% of an antiperspirant active.

6. A deodorant gel stick composition comprising: a. from 0.05% to 10% intermediate ratio Si0₂/Al₂0₃ ultrastable Y zeolite; b. from 60% to 90% of a liquid material; c. from 1% to 30% of a solidifying agent; and d. from 5% to 50% of a deodorant active.

7. The process for making cosmetic compositions essentially free of material malodors wherein after the odoriferous cosmetic base is combined and liquified, the zeolitic material is added and distribute uniformly through out the liquified odoriferous cosmetic base.