KR19990007904A - Personal topical care compositions containing alkenyl or styrene end-capped silicone grafted copolymers - Google Patents

Abstract

The present invention provides an aqueous or hydroalcoholic carrier, characterized in that the hydrolysis of the silicone portion of the copolymer, which can be obtained by introducing a silicone macromer of the selected type into the silicone grafted copolymer, is substantially improved or reduced. A personal topical care composition containing a silicone grafted copolymer and an acid-containing monomer. The silicone macromers are selected from the group consisting of alkenyl end-capped silicone macromers and styrene-end capped silicone macromers and combinations thereof. Silicone macromers are ethylenically unsaturated polymerizable monomers having styrene or alkenyl end-capped silicone groups covalently bonded to the ethylenically unsaturated portion of the monomer via styrene or alkenyl end-caps.

Description

Personal topical care compositions containing alkenyl or styrene end-capped silicone grafted copolymers

It is well known to use silicone grafted copolymers in various topical care compositions, such as hair and skin care compositions. The polymers are useful because they have film formability and adhesion and can be used as adhesives in a variety of skin care products such as hair sprays, mousses and lotions as well as cosmetics and skin conditioning compositions. Here, film forming properties are used to smooth the skin or to help other ingredients to be delivered to the skin. One of the most important advantages of silicone grafted copolymers is that the silicone moiety provides an improved feel compared to conventional polymers. For example, hair treated with the polymer is softer to the touch than hair styled with conventional hair styling polymers while maintaining a style that is styled to the user's intention. Skin treated with a silicone grafted polymer is smoother to the touch than skin treated with conventional polymers.

One of the most preferred and inexpensive methods of using silicone grafted copolymers is to combine them into aqueous or hydroalcoholic carriers. Wherein the silicone grafted copolymer is soluble or stably dispersed in the aqueous / hydroalcohol system. Another preferred type of composition provides a silicone grafted copolymer that is emulsified in the form of droplets dissolved in a non-aqueous solvent such as cyclomethicone or hydrocarbon and dispersed throughout an aqueous or hydroalcoholic carrier. This type of formulation is useful and desirable for many types of products, but it is more desirable to use silicone grafted copolymers that are soluble or stably dispersed in non-dropletized forms that are unemulsified in aqueous or hydroalcoholic carriers in many other products. Desirable and less expensive.

One of the preferred silicone grafted copolymers for use in personal aqueous topical care compositions, especially hair spray compositions, contains acrylic acid monomers and methacryloxy propyl end-capped silicone macromers. It is highly desirable to use acrylic acid monomers because acid groups provide a high degree of polarity, making the polymer soluble or dispersible in aqueous or hydroalcoholic carriers. Other highly polar monomers such as many cationic monomers can provide similar solubility to the polymer but tend to be more hygroscopic. As a result, the product becomes tacky during use, especially under humid conditions. Unfortunately, it has been found that these silicone grafted copolymers are hydrolyzed to an undesirably high degree in aqueous or hydroalcoholic products such that the silicone portion tends to separate from the rest of the copolymer. Similar copolymers containing the same type of silicone macromers and no acrylic acid monomers are not so hydrolyzed. Therefore, it appears surprisingly that hydrolysis problems occur only when the polymer contains acrylic acid or other acid-containing monomers.

Hydrolysis is of interest because various products contain water as the main solvent or cosolvent for hair styling polymers and other hair and skin care adhesive polymers. Hydrolysis is of particular interest given the current trend of developing products with high moisture content and reduced levels of volatile organic compounds (VOC's). Of particular interest is the tendency to limit the level of VOC's in current products, for example, to 55% and 80%, the VOC limit lines already present in many countries. As the trend to develop personal topical care products with reduced VOC's levels continues, some or all of the VOC-based formulations will be replaced by aqueous and hydroalcoholic formulations.

It is an object of the present invention to provide aqueous and hydroalcohol-based personal topical care compositions containing silicone grafted copolymers with improved stability against hydrolysis. It is also an object of the present invention to provide a composition as described above which may contain acrylic acid or other acid-containing monomers in the silicone grafted polymer or impart to the product the properties found in the polymer. Another object of the present invention is to provide a composition that meets the above objectives and has a relatively low or zero level of volatile organic compounds. These and other advantages of the present invention, apparent to those skilled in the art, may be obtained by the invention described below.

Unless stated otherwise, all percentages are calculated by weight of the total composition and all ratios are calculated by weight. Unless stated otherwise, the amounts of ingredients are based on activity levels and therefore do not include carriers or by-products that may be included in commercially available or otherwise available materials. The present invention may include, consist of, or consist essentially of the essential and various optional and / or preferred components and elements described herein. The terms soluble and insoluble refer to the dissolution properties of a particular component in the composition unless otherwise indicated. All viscosity and solubility are determined at 25 ° C. unless stated otherwise. Also, unless stated otherwise, all weight percentages of the compositions herein are based on the total weight of the composition, excluding any propellant that may be incorporated into the product or otherwise contemplated.

Summary of the Invention

Personal topical care compositions containing aqueous and hydroalcoholic carriers and silicone grafted polymers can be obtained according to the invention, characterized in that the problem of hydrolysis of the silicone part of the copolymer is substantially improved or solved. It has been found that the composition can be obtained by combining certain types of silicone macromers with acid-containing monomers for incorporation into the silicone grafted copolymer. The silicone macromers herein are selected from the group consisting of alkenyl end-capped silicone macromers and styrene end-capped silicone macromers and combinations thereof. Silicone macromers are ethylenically unsaturated polymerizable monomers having styrene or alkenyl end-capped silicone groups covalently bonded to the ethylenically unsaturated portion of the monomer via styrene or alkenyl end-caps.

The compositions herein can be used in a variety of personal topical care applications such as hair care, skin care, cosmetics and personal cleansing compositions. They are particularly useful for hair styling products such as hair sprays, hair lotions, hair tonics, mousses, hair rinses and shampoos. Other specific uses for which this product is useful include skin care compositions, such as skin moisturizers and other skin conditioning compositions, sunscreens, sunless tanning compositions, skin cleansing compositions, acne treatment compositions, topical analgesics and other drug-containing Topical skin compositions are included. Skin care compositions also include cosmetics.

More specifically, the present invention provides a composition comprising (a) from about 1% to about 99, based on the weight of the silicone grafted copolymer, wherein the acid moiety is preferably selected from the group consisting of carboxylic acids, sulfonic acids, and combinations thereof. % Acid-containing monomers; (ii) from about 1% to about 50% silicone macromers having the following Formula 1 or 2 and combinations thereof; (iii) from about 0.1% to about 50% silicon grafted copolymer, based on the weight of the composition, containing 0% to 98% of additional monomers and combinations thereof; And (b) from about 1% to about 99.9% by weight of the silicone grafted copolymer, based on the weight of the composition, suitable for application to hair or skin, capable of dissolving or dispersing the copolymer. A personal topical care composition comprising a silicone grafted copolymer having improved stability against hydrolysis, comprising a solvent based:

In the above formula,

s is an integer from 0 to about 6;

m is an integer from 1 to 3;

R ² is C ₁ -C ₁₀ alkyl or C ₇ -C ₁₀ alkylaryl;

n is an integer from 0 to 4;

X is a chemical formula An ethylenically unsaturated group of wherein R ³ is H or C ₁ -C ₆ alkyl and R ⁴ is H or C ₁ -C ₆ alkyl;

Z is a chemical formula Wherein each R ¹ is independently alkyl, aryl or alkylaryl having 1 to 10 carbon atoms, and r is an integer from about 4 to about 700.

The invention will be described in more detail in the following description of the invention.

The present invention relates to a personal topical care composition containing an aqueous or hydroalcoholic carrier suitable for application to the skin or hair and a silicone grafted copolymer soluble or dispersible in a continuous phase of the carrier. .

The personal topical compositions of the invention generally comprise (a) about 0.1% to about 50%, preferably about 0.2% to about 20%, more preferably, styrene or alkenyl end-capped silicone grafted copolymer Preferably from about 0.5% to about 15%, even more preferably from about 1% to about 10%, most preferably from about 2% to about 8%; (b) about 1% to about 99.9% by weight, preferably about 50% to about 99.8% by weight of an aqueous or hydroalcoholic solvent for a silicone grafted polymer suitable for application to hair or skin 60% to about 99.5%, even more preferably about 70% to about 99%, most preferably about 80% to 98%. Silicone grafted copolymers are soluble or dispersible in aqueous or hydroalcoholic solvents.

Personal topical care compositions herein refer to those suitable for topical application to skin or hair. The term suitable for topical application to the skin or hair is safe for topical application to the skin or hair when the composition is used according to the intended method and the copolymer in the composition is applied to the skin or hair such that the copolymer provides its intended benefit. Say something that is effective to convey.

Aqueous or hydroalcohol solvents

The aqueous or hydroalcoholic solvent for the copolymers of the present invention may be water or at least one monovalent C ₁ -C ₆ alcohol, preferably C ₂ -C ₃ alcohol, more preferably C ₂ alcohol (ie ethanol) with water. ) May be a combination. The total level of aqueous or hydroalcohol solvents is described above. Hydroalcohol system refers to any mixture of one or more alcohols and water, containing at least about 0.5% water by weight of the solvent.

Generally, however, for hair care products such as hair sprays and mousses, the composition generally comprises at least about 5% water, preferably at least about 10% water, more preferably at least about 20% water.

In another embodiment of the invention, the composition is characterized by having a reduced level of volatile organic compounds (VOC's), wherein from about 40% to about 99.9% water and 0% to about 80%, preferably 0% To about 55% monohydric alcohol. In a particularly preferred embodiment of the aerosol or non-aerosol hair spray composition, the composition comprises about 40% to about 75% water and about 20% to about 55% monohydric alcohol, or about 40% to about 95% water and zero % To about 55% monohydric alcohol. In reduced VOC compositions, the total level of VOC's is preferably about 80% or less, preferably about 55% or less, based on the weight of the composition including the propellant.

For the purposes of the present invention, VOC's are defined as any organic compound (including silicon) having a vapor pressure of at least 0.1 mmHg or containing up to 12 carbon atoms at 20 ° C. Conversely, an organic compound having a vapor pressure of less than 0.1 mm Hg or containing more than 12 carbon atoms under the same conditions is defined herein as nonvolatile.

The styrene and alkenyl end-capped silicone grafted copolymers herein are soluble or dispersible in aqueous or hydroalcoholic solvents. This is in contrast to the case where the copolymer is soluble or not dispersible in the solvent and therefore exists as a separated phase or discontinuous phase from the solvent.

Additional solvents, cosolvents, and dissolution aids may be incorporated into the compositions herein to assist in dissolution of the copolymer without departing from the spirit or intent of the present invention. Examples of such components include, but are not limited to, dihydric and trihydric alcohols, surfactants, and emulsifiers.

Styrene / alkenyl end-capped silicone grafted copolymer

Silicone grafted copolymers (hereinafter sometimes referred to as copolymers) form an essential component of the present invention. The term copolymer as used herein refers to a polymer derived by polymerizing two or more different kinds of monomers. Copolymers herein are prepared by copolymerizing one or more types of acid-containing monomers, one or more specific styrene or alkenyl end-capped silicone macromers (or mixtures thereof) and optionally one or more other types of monomers. For convenience, the copolymers herein are sometimes described as derived from the monomers and macromers, meaning that the copolymers are prepared by copolymerization of the monomers and macromers. As used herein, the term monomer refers to an ethylenically unsaturated compound capable of polymerizing to form a copolymer as defined herein. The term macromer, as used herein, refers to a monomer characterized by having a polymeric substituent. An essential macromer of the present invention is a silicone macromer, which means that the macromer has silicone as the polymeric substituent. In addition, when the copolymers herein are sometimes described as comprising the monomers and macromers, this means that the copolymers comprise units corresponding to the indicated pre-polymerized monomers and macromers.

Acid-containing monomers

The copolymers herein comprise about 1% to about 99% acid-containing monomer by weight of the copolymer. Generally the copolymer will contain from about 5% to about 90%, more preferably from about 10% to about 80%, most preferably from about 15% to about 75% of the acid-containing monomer. The particular level of acid-containing monomer desired for any particular composition will depend on the type of combination and intended use as well as the amount of other monomers and macromers in the copolymer and the molecular weight of the copolymer. For hair sprays and other hair care compositions, for example, the copolymer is preferably from about 5% to about 50%, more preferably from about 10% to about 35%, most preferably based on the weight of the copolymer From about 15% to about 25% of the acid-containing monomer.

The acid-containing monomer is preferably selected from acid groups selected from the group consisting of carboxylic acids and sulfonic acids, most preferably monomers containing carboxylic acid groups. Other acid-containing monomers are also used and include, but are not limited to, phosphoric acid-containing monomers. Combinations of these types of acid-containing monomers may also be used.

The acid-containing monomer units present in the final copolymer can be derived from polymerizable acid-containing starting monomers or from polymerizable nonionic monomers which can then be modified to have acid functionality after polymerization. Also included within the term acid-containing monomers are neutralizations, i.e. salts of monomers. Neutralization will be described in more detail later.

Examples of acid-containing monomers include the following:

(i) carboxylic acid-containing monomers comprising those corresponding to the formula:

Wherein R ⁵ and R ⁶ are independently H or C ₁ -C ₆ alkyl, preferably H or methyl; R ⁷ represents H, C ₁ -C ₆ alkyl or up to about 12 carbon atoms Having a carboxylic acid residue, preferably H or methyl, or when R ⁷ is a carboxylic acid residue, preferably acrylic acid, R ⁸ is a carboxyl residue having up to about 12 carbon atoms);

Specific examples of carboxylic acid-containing monomers include acrylic acid, methacrylic acid, maleic acid, maleic acid half esters, itaconic acid, fumaric acid and crotonic acid; Semiesters of polyhydric acid anhydrides such as succinic anhydride, phthalic anhydride, etc., which react with hydroxy group-containing acrylates and / or methacrylates such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, etc. Included.

(ii) sulfonic acid-containing monomers such as styrenesulfonic acid, sulfoalkyl acrylates and methacrylates, preferably those having C ₁ -C ₆ alkyl groups, more preferably C ₂ alkyl groups, for example sulfo Ethyl acrylate and sulfoethyl methacrylate and the like;

(iii) phosphoric acid-containing monomers such as phospho oxyalkyl acrylates and methacrylates, preferably C ₁ -C ₆ oxyalkyl groups, more preferably C ₁ -C ₃ oxyalkyl groups. Specific examples include phospho-oxyethyl acrylate, phospho-oxyethyl methacrylate, 3-chloro-2-acid phospho-oxypropyl acrylate, phospho-oxypropyl methacrylate and the like.

Preferred acid-containing monomers are carboxylic acid and sulfonic acid. Carboxylic acids are most preferred. Examples of highly preferred acid-containing monomers are acrylic acid, methacrylic acid and styrenesulfonic acid. Particularly preferred acid-containing monomers are acrylic acid and methacrylic acid.

Styrene and alkenyl end-capped silicone macromers

The copolymers herein comprise from about 1% to about 50%, preferably from about 2%, to styrene end-capped silicone macromers, alkenyl end-capped silicone macromers, or a combination thereof based on the weight of the copolymer. About 40%, more preferably about 5% to about 40%, most preferably about 5% to about 25%. Styrene or alkenyl end-capped silicone macromers refer to macromers containing silicone, ie, polymeric siloxane or polysiloxane groups, covalently bonded to monomers via styrene or alkenyl groups, respectively.

Preferred styrene end-capped silicone macromers and alkenyl end-capped macromers of the present invention each have the formula:

Formula 1

Formula 2

In the above formula,

s is an integer from 0 to about 6, preferably 0, 1 or 2, more preferably 0 or 1;

m is an integer from 1 to 3, preferably 1;

R ² is C ₁ -C ₁₀ alkyl or C ₇ -C ₁₀ alkylaryl, preferably C ₁ -C ₆ alkyl or C ₇ -C ₁₀ alkylaryl, more preferably C ₁ -C ₂ alkyl;

n is an integer from 0 to 4, preferably 0 or 1, more preferably 0;

X is a chemical formula An ethylenically unsaturated group of (before polymerization) wherein R ³ is H or C ₁ -C ₆ alkyl, preferably H or C ₁ -C ₂ alkyl, more preferably H; R ⁴ is H Or C ₁ -C ₆ alkyl, preferably H or C ₁ -C ₂ alkyl and more preferably H or methyl);

Z is a chemical formula (Wherein R ¹ is each independently alkyl, aryl or alkylaryl having 1 to 10 carbon atoms, preferably C ₁ -C ₆ alkyl, more preferably C ₁ -C ₂ alkyl, most preferred Preferably methyl; r is an integer from about 4 to about 700, preferably from about 50 to about 500, and more preferably from about 100 to about 300). For hair care compositions such as hair sprays, r is most preferably about 150 to about 200. Styrene-terminated capped silicone macromers are preferred.

The silicon portion of the macromer is preferably substituted at the para or meta position of the aromatic ring with respect to X, most preferably at the para position. If n is not zero, the R ² group (s) are preferably substituted at the meta position. The ortho position is preferably not substituted but need not be.

Styrene and alkenyl end-capped silicone macromers and methods of making them are well known in the art. See, eg, Holohan, George, Barrie, Parker, for example, which discloses silicone macromers where s is 0 for styrene end-capped macromers and s is 0 or an integer for alkenyl end-capped silicone macromers. Monofunctional Polydimethylsiloxane Oligomers For Graft Copolymerization, Macromol. Chem. Phys. 195, 2965-2979 (1994). Further details regarding the preparation of the silicone macromers are in the experimental section later.

Additional monomers

Generally, the copolymers herein contain from 0% to about 98%, preferably 0%, based on the weight of the copolymer, in addition to the acid-containing monomers described above and additional monomers in addition to styrene or alkenyl end-capped silicone macromers. About 80%, more preferably 20% to about 70%. In the case of hair care compositions such as hair sprays, the copolymer preferably comprises from 40% to about 70% additional monomers. As will be described in more detail below, the use of additional monomers increases the T _g of the copolymer, or the solubility of the copolymer depending on the specific type and level of the other copolymer and the type and amount of the aqueous or hydroalcoholic solvent. It may be particularly desirable to control. When using additional monomers in whole or in part for one or both of the above purposes, the additional monomers are generally at least about 1%, more generally at least about 2%, preferably based on the weight of the copolymer. At least about 5%, more preferably at least about 10%.

Various additional monomers can be used. This includes nonionic monomers, cationic monomers and amphoteric monomers. Nonionic monomers may include low or high polar monomers. Cationic monomers can be polymerized in a cationic state and can be polymerized as a nonionic precursor and then quaternized or otherwise modified to cationic after polymerization. When cationic monomers are used, the weight percent of at least one cation or acid-containing monomer is preferably about 10% or less, preferably about 5% or less, in order to minimize the occurrence of ionic interactions between the two charged groups. Do.

Examples of low polar nonionic monomers include methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol , t-butanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3, 5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, oleyl alcohol, isobor Acrylic acid and methacrylic acid esters of C ₁ -C ₂₄ alcohols, alcohols having an average of about 1 to 18, more preferably about 1 to 12 carbon atoms, such as nil alcohol, tetrahydrofurfuryl alcohol, and the like; Styrene; Alkyl styrene, preferably C ₁ -C ₆ alkylstyrene, such as t-butylstyrene; Chlorostyrene; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl chloride; Vinyl toluene; Vinyl caprolactam; Vinylidene chloride; Acrylonitrile; C ₁ -C ₆ alkylstyrenes such as alpha-alkylstyrene, preferably alpha-methylstyrene; 1,3-dialkenes such as butadiene and cyclohexadiene; Ethylenically unsaturated hydrocarbons, preferably C ₁ -C ₅ alkenes such as ethylene and propylene; Alkoxyalkyl (meth) acrylates, preferably alkoxy C ₁ -C ₆ alkyl (meth) acrylates such as methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate; And C ₁ -C ₆ alkyl vinyl ethers, such as alkyl vinyl ethers, preferably methyl vinyl ethers. Other low polar nonionic monomers include acrylate and methacrylate derivatives such as di-acrylate and di-methacrylate, for example ethylene glycol di-acrylate, ethylene glycol di-methacrylate, 1,3-butyl Leneglycol di-acrylate and -methacrylate; And diacetone acrylamide. As used herein, (meth) acrylate refers to both acrylates and methacrylates.

Preferred low polar nonionic monomers include n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate and combinations thereof. Included.

Examples of high polar nonionic monomers include acrylamide; Methacrylamide; N, N-dialkyl (meth) acrylamides, particularly preferably N, N-diC ₁ -C ₆ alkyl (meth) acrylamides such as N, N-dimethylacrylamide; N-alkyl acrylamides, especially NC ₁ -C ₆ alkyl acrylamides such as Nt-butyl acrylamide and isopropylacrylamide; Acrylate and methacrylate alcohols, in particular C ₂ -C ₆ (meth) acrylate alcohols such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; Vinyl pyrrolidone, allyl alcohol and vinyl alcohol (prepared by polymerizing and then hydrolyzing vinyl acetate).

Cationic monomers include quaternizable amino-functional ethylenically unsaturated monomers such as (meth) acrylates such as styrene, acrylamide, methacrylamide, C ₁ -C ₅ alkyl esters of acrylic acid and methacrylic acid Amino functional derivatives of the present invention. Preference is given to C ₁ -C ₅ alkyl amines, in particular C ₁ -C ₃ amines. It is preferred to use tertiary amines (eg trialkyl amines), but it is not necessary to exclude monoalkyl amines, dialkyl amines and other alkyl amine derivatives. Dimethyl amino C ₁ -C ₃ alkyl amines are particularly preferred. The monomers can be quaternized before and after polymerization, preferably after polymerization.

Cationic monomers include (i) quaternized epihalohides of monomers derived from acrylic acid or methacrylic acid collectively referred to as (meth) acrylic acid, and trialkylamines having from 1 to 5 carbon atoms in alkyl. Broughtin products such as (meth) acryloxypropyltrimethylammonium chloride and (meth) acryloxypropyltriethylammonium bromide; (ii) amine derivatives of (meth) acrylic acid or amine derivatives of (meth) acrylamide derived from (meth) acrylamide or (meth) acrylic acid, and dialkylalkanolamines having C ₁ -C ₄ alkyl groups, eg For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate or dimethylaminopropyl (meth) acrylamide; And (iii) a derivative derived by (1) neutralizing the product of group (ii) with an acid such as hydrochloric acid or lactic acid, (2) alkylation of the product of group (ii) with halogenated alkyls such as methyl chloride, ethyl chloride , Derivatives derived by modification with methyl bromide or ethyl iodide, (3) derivatives obtained by modifying said product of group (ii) with halogenated fatty acid esters such as ethyl monochloroacetate or methyl monochloropropionate, and ( 4) derivatives derived by modifying the product of group (ii) with dialkyl sulfates such as dimethyl sulfate or diethyl sulfate.

Specific examples of such monomers include (i) p-dimethylaminomethyl styrene, p-dimethylaminoethyl styrene; (ii) dimethylaminomethyl acrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminomethyl methacrylamide; Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide. Cationic monomers also include amine derivatives of allyl compounds such as diallyldimethylammonium chloride and the like.

As mentioned above, cationic monomers are polymerized in cationic form, or alternatively, they are polymerized as precursors and then cationic, for example, using quaternizing agents (eg ethyl monochloroacetate, dimethyl sulfate, etc.). It can be modified to sex.

Examples of amphoteric monomers include dimethylaminoethyl (meth) with halogenated fatty acid salts such as potassium monochloroacetate and sodium monobromopropionate, aminomethylpropanol salts of monochloroacetic acid, triethanolamine salts of monochloroacetic acid, and the like. Zwitterionic derivatives of (meth) acrylamide or amine derivatives of (meth) acrylic acid, such as acrylate, dimethylaminopropyl (meth) acrylamide; And amine derivatives of (meth) acrylic acid or (meth) acrylamide modified with propanesultone as described above.

As with the cationic monomers described above, the amphoteric monomers can be polymerized in an amphoteric form, or alternatively they can be polymerized as precursors and then converted to amphoteric.

Copolymer

The copolymers herein must have a weight average molecular weight of at least about 20,000 to provide effective adhesion or film formation to the hair or skin. There is no upper limit to the molecular weight except when there is a limit to the applicability of the present invention for practical reasons such as processing, aesthetic properties, blendability, and the like. Generally, the weight average molecular weight will be less than about 10,000,000, more generally less than about 5,000,000, preferably less than about 3,000,000. Preferably, the weight average molecular weight is about 50,000 to about 2,000,000, more preferably about 75,000 to about 1,000,000, most preferably about 100,000 to about 750,000. The molecular weight can be determined by gel permeation chromatography calibrated by refractive index and differential viscometer measurements using polystyrene standards or equivalents thereof.

Preferably, the copolymers of the present application have a T _g of about −20 ° C. or higher, preferably about 20 ° C. when dried to form a film, so they are not excessively tacky and non-sticky. Preferably, T _g is about 20 ° C to about 120 ° C. As used herein, the abbreviation T _g is the glass transition temperature of the non-silicone backbone of the copolymer. T _g can be measured by methods well known in the art, such as differential scanning calorimetry (DSC) or dynamic mechanical analysis. T _g can be adjusted by varying the level and type of various acid-containing monomers and additional monomers used.

Methods of making silicone grafted copolymers are well known in the art. The silicone grafted copolymers of the present invention can be prepared according to known methods, but the addition that the starting monomer should be selected such that the final product contains an styrene end-capped silicone macromer with an acid-containing monomer as described above. The requirements of Examples of methods for making silicone grafted polymers are described in U.S. Patent No. 4,693,935 to Mazurek, Sep. 15, 1987, incorporated herein by reference, in Clemens, Mar. 1, 8, 198. U.S. Patent 4,728,571 to U.S. Patent No. 5,061,481 to Suzuki et al. On October 29, 1991, U.S. Patent No. 5,219,560 to Suzuki et al. On June 15, 1993, 1992 U.S. Patent No. 5,166,276 to Hayama et al., Dated Nov. 24, 1992, and U. S. Patent No. 5,106,609, issued March 31, 1992 to Bolich et al., April 21, 1992. U.S. Patent No. 5,100,658 to Ritchie et al., U.S. Patent No. 5,100,657 to March 31, 1992, US Patent No. 5,100,657 to April 17, 1992, and B. U.S. Patent No. 5,104,646, February 4, 1994 to Torgerson To EPO 0 412 707, Bolich et al., Published February 13, 1991, EPO 0 412 704, published on 18 August 1992 by Pepply's EPO Application No. 92918969.4, 8 1992. EPO Application No. 92918839.9 et al. Filed May 18, and EPO Application No. 92919224.3, filed August 18, 1992.

In general, the copolymers of the present invention can be prepared by free radical polymerization of silicone macromers with acid-containing monomers and other monomers that may be used. The general principles of the free radical polymerization process will be understood. See, eg, Odian, Principles of Polymerization, 2nd edition, John Wiley Sons, 1981, pp. 179-318. Preferred monomers are added to the reactor with a sufficient amount of solvent so that the viscosity of the reactants is justified at the end of the reaction. Typical monomer feeds are from about 20% to about 50%. If necessary, unnecessary terminators, especially oxygen, are removed. This can be done by purging or evaporating with an inert gas such as argon or nitrogen. An initiator is introduced and the reaction is brought to the temperature required for initiation to take place to achieve the same effect as using a thermal initiator. Another method uses redox or radiation initiation as described above. Typically the polymerization is carried out to the extent necessary for a high level of conversion to take place over several hours to several days. The solvent is then removed, usually by evaporation or by precipitation of the copolymer by addition of a nonsolvent. The polymer is further purified as necessary.

The copolymers herein are preferably used in at least partially neutralized form. Neutralization can improve the solubility or dispersion of the polymer in the composition. Neutralization also assists in removing the copolymer from the hair or skin when the hair or skin is washed with shampoos, soaps, detergents or other cleaning products. In general, it is preferred that about 10% to 100%, more preferably about 20% to about 90%, even more preferably about 40% to about 85% of the acid functionality of the polymer is neutralized.

Any conventionally used base, organic or metallic material can be used for neutralization. Hydroxides of alkali metals and alkaline earth metals are preferred neutralizers for use with silicon grafted copolymers. Preferred neutralizing agents for use in the hair spray compositions of the invention are potassium hydroxide and sodium hydroxide. Examples of other suitable neutralizing agents that can be used include amines, in particular amine alcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol ( AEPO), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), mono Isopropanolamine (MIPA), diisopropanol-amine (DIPA), triisopropanolamine (TIPA) and dimethyl steamine (DMS). Mixtures of amines and bases (metallic or organic materials) can also be used.

If unreacted silicone macromers are present at undesirably high levels and may impair the performance of the product, they may be removed by methods well known in the art. One method that can be used is a supercritical fluid extraction method such as supercritical carbon dioxide. Another generally applicable method is membrane separation performed according to standard methods in the art.

Purification methods that may be particularly useful for the copolymers herein are solvent extraction methods using nonpolar solvents. Suitable solvents include C ₃ -C ₈ hydrocarbons, preferably C ₅ -C ₆ hydrocarbons such as hexane. Prior to performing the extraction, the polymer reaction product is precipitated from the reaction solvent (eg using water) and dried. The extraction solvent is preferably heated to a temperature near or slightly above the average T _g of the non-silicone backbone portion of the polysilicon-grafted polymer of the adhesive. The temperature should be high enough to soften the polymer but not high enough to solidify the polymer. The extraction solvent and reaction product can be mixed before and after heating the solvent. The extraction solvent and the polymer reaction product should be mixed for a time sufficient to remove the soluble material, preferably in the presence of excess solvent. The time will depend on the reflux temperature of the solvent, the T _{g of the} copolymer, the temperature at which the solvent is actually heated, the desired level of removal of low viscosity materials and unreacted monomers remaining after polymerization, and the number of solvent extraction cycles to be performed. . Typically, the solvent extraction time is about 30 minutes to about 2 hours and more typically about 30 minutes to about 1 hour. The solvent is removed by conventional methods, such as decantation, filtration, etc. while drying or distilling for each cycle to remove traces of extraction solvent remaining in the product after the final extraction cycle.

Analysis of polymer reaction products, extracted materials and purified film formers can be carried out by conventional analytical methods known in the art. This includes, for example, wet methods such as nuclear magnetic resonance (NMR), infrared molecular spectroscopy, gel permeation / size exclusion chromatography, liquid chromatography, gas chromatography, atomic absorption and emission spectroscopy and titration.

Personal topical care compositions

Various personal topical care compositions are contemplated under the present invention, including hair care compositions and skin care compositions. Hair care compositions include hair sprays (aerosols and non-aerosols), hair tonics, hair lotions, shampoos, hair rinses and mousses. Skin care compositions include skin moisturizers and other skin conditioning compositions, sunscreens, sun tanning compositions, skin cleansing compositions, acne treatment compositions, topical analgesics and other drug-containing topical skin compositions, and the like. Skin care compositions also include cosmetics and fragrances, especially those used on the face. Cosmetics include, for example, foundations; Eye makeup such as mascara; And lip makeup. Fragrances include perfumes, colognes, and after-shaves.

The personal topical care compositions of the present invention include products in which copolymers are used as adhesives for styling hair for the purpose of modifying the skin surface for skin conditioning purposes or for cosmetic appearance. The copolymers herein can also be used to facilitate delivery of the active ingredient to hair or skin. By curing the above components by the adhesive film which can be formed by the copolymer of the present invention at the time of curing, the identity to skin or hair can be improved. Examples of such active ingredients include the selective absorption of drugs, cosmetic active ingredients (eg dyes and pigments for hair or skin conditioners, cosmetics, perfumes and fragrances, etc.), sunscreens (UV-A and / or UV-B rays). Chemical sunscreens to protect skin or hair, as well as physical sunscreen active ingredients such as zinc dioxide or titanium dioxide) and sunless tanning agents.

The compositions herein can provide any desired benefit without unduly disrupting the action of styrene end-capped silicone grafted copolymers as well as any components typically known to be used in the desired type of product. It may be blended to include other ingredients. Non-limiting examples of various ingredients for use in personal topical care compositions are described below.

Personal topical care compositions include hydrocarbons (eg isobutane, hexane, decene), halogenated hydrocarbons (eg freon), linalool, esters (eg ethyl acetate, dibutyl phthalate), and volatile silicone derivatives. (Especially siloxanes such as phenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane Cyclomethicone, and polydimethyl siloxanes such as dimethicone having a viscosity of about 15 centipoise at 25 ° C. or less) and mixtures thereof, and various volatiles. Volatile materials such as these are commonly used in topical compositions such as sprays, tonics, gels and mousses.

Personal aerosol topical care compositions, such as mousse and aerosol hair sprays, can use any conventional propellant to deliver the substance. Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. Aerosol spray products as well as aerosol sprays may contain surfactants to enhance sprayability. Examples of suitable surfactants may include nonionic, cationic, anionic surfactants or mixtures thereof. Fluorosurfactants are included herein. Surfactants are particularly preferred for the spray products of the present invention, in particular spray products such as hair sprays, and the sprayability can affect product performance because the composition has a relatively low level of volatile organic compounds and a relatively high level of water. to be. High levels of water of the compositions of the present invention can negatively affect spraying in other ways. If such a surfactant is used, it is preferably present at from about 0.01% to about 7.5% by weight of the total composition. The level of propellant can be adjusted to the extent desired. Propellants are generally from about 3% to about 30% of the mousse composition and from about 15% to about 50% of the aerosol hair spray composition based on the total weight of the composition (including the weight of the propellant). The propellant levels of other products can vary widely, but are generally from about 3% to about 70% by weight of the total composition.

Suitable spray containers are well known in the art and include conventional aerosol pump sprays (ie sprayers), aerosol containers or cans with propellants as described above, and pump aerosol containers using compressed air, such as propellants. . Pump aerosol containers are described, for example, in U.S. Patent No. 4,077,441 to Olofsson, March 7, 1978, which is incorporated herein by reference, and United States, to TerStege, July 25, 1989. Goslin, dated February 21, 1992, was Patented 4,850,577 and Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles. ), Lund, Sojka and Lefebvre, which are disclosed in US Patent Application Ser. No. 07 / 839,648. Pump aerosol hair sprays using compressed air are also commercially available from The Procter & Gamble Company as the VIDAL SASSOON AIRSPRAY ^R hair spray.

The composition of the present invention may have various forms. For example, the silicone grafted copolymer can be a single phase composition as well as an emulsion present on the aqueous or hydroalcoholic phase of the emulsion. Examples of emulsions include oil-in-water, water-in-oil, water-in-oil-in-water, and silicon-in-water oil. -in-water-in-silicone emulsions, including but not limited to. The silicone grafting copolymer will be present on the aqueous or hydroalcoholic phase of the composition.

The composition may have a range of viscosities, preferably from about 1 cS to about 200,000 cS at 25 ° C.

Additional ingredients

Various additional ingredients can be used in the personal topical care compositions herein. Non-limiting examples include the following:

Pharmaceutically active ingredients

The composition of the present invention may comprise a safe and effective amount of the pharmaceutically active ingredient. As used herein, a safe and effective amount refers to an amount of active ingredient that is high enough to substantially or positively improve the condition to be treated but low enough to avoid serious side effects (a reasonable benefit / risk ratio) within the appropriate medical judgment. Safe and effective amounts of pharmaceutically active ingredients include the specific active ingredient, the ability of the composition to penetrate the active ingredient through the skin, the amount of the composition applied, the particular condition to be treated, the age and physical condition of the patient to be treated, the severity of the condition, the treatment It will depend on the duration, nature of the current therapy and similar factors.

Pharmaceutically active ingredients that can be used in the compositions of the present invention preferably comprise about 0.1% to about 20%, more preferably about 0.1% to about 10%, most preferably about 0.1% to 5% of the composition. can do. Mixtures of pharmaceutically active ingredients can also be used.

Non-limiting examples of pharmaceutically active ingredients can include the following.

Pharmaceutically active ingredients useful in the compositions of the present invention include acne treatments. Preferred acne treatments for use in the present invention include keratolytic agents such as salicylic acid, sulfur, lactic acid, glycolic acid, pyruvic acid, urea, resorcinol and N-acetylcysteine; Retinoids such as retinoic acid and derivatives thereof (eg cis and trans); Antibiotics and antibacterial agents such as benzoyl peroxide, octopyrox, erythromycin, zinc, tetracycline, triclozan, azelaic acid and derivatives thereof, phenoxy ethanol and phenoxy propanol, ethyl acetate, clindamycin and meclocycline; Sebostats such as flavinoids; Alpha and beta hydroxy acids; And bile acids such as sinol sulphate and derivatives thereof, deoxycholate and cholate. Preferred for use herein is salicylic acid.

Pharmaceutically active ingredients useful in the compositions of the present invention include non-steroidal anti-inflammatory agents (NSAIDS). NSAIDS is a propionic acid derivative; Acetic acid derivatives; Phenoic acid derivatives; Biphenylcarboxylic acid derivatives; And oxycams. All NSAIDS are fully described in US Pat. No. 4,985,459, issued to Sunshine et al. On January 15, 1991, incorporated herein by reference. Aspirin, acetaminophen, ibuprofen, naproxen, venoxapropene, flubiprofen, phenopropene, fenbufen, ketoprofen, indoprofen, fipropene, caprophene, oxaprozin, pranoprofen, Most preferred are propionic NSAIDS, including but not limited to myroprofen, thioxapropene, suprofen, aminopropene, thiapropenic acid, flupropenic acid and buclinic acid. Also useful are steroidal anti-inflammatory agents, including hydrocortisone and the like.

Pharmaceutically active ingredients useful in the compositions of the present invention include ginseng. Preferred anti-inflammatory agents for the compositions of the present invention include pharmaceutically acceptable salts of metrelizine and trimetaprazine. Pharmaceutically active ingredients useful in the compositions of the present invention include anesthetics. Preferred anesthetics for inclusion in the compositions of the present invention include lidocaine, bupivacaine, chlorprocaine, dibucaine, ethidocaine, mepivacaine, tetracaine, diclonin, hexylcaine, procaine, cocaine, ketamine, praca And pharmaceutically acceptable salts of phenol and phenol. Pharmaceutically active ingredients useful in the compositions of the present invention include antibacterial agents (antibacterial agents, antifungal agents, probiotic and antiviral agents). Preferred antibiotics for inclusion in the compositions of the present invention are b-lactams, quinolines, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, triclozan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, Oxytetracycline, clindamycin, etabutol, metronidazole, pentamidine, gentamicin, kanamycin, linenemycin, metacycline, metenamin, minocycline, neomycin, netylmycin, palomomycin, streptomycin, tobramycin, myconazole and myconazole Pharmaceutically acceptable salts of amanpaddine. Preferred antibiotics to be included in the compositions of the present invention include tetracycline hydrochloride, erythromycin estolate, erythromycin stearate (salt), amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chlorhexidine hydro Chloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycin hydrochloride, metacycline hydrochloride, methene Namin hypofurate, methenamin mandelate, minocycline hydrochloride, neomycin sulfate, Tylmycin Sulfate, Paromomycin Sulfate, Streptomycin Sulfate, Tobramycin Sulfate, Myconazole Hydrochloride, Amanfadine Hydrochloride, Amanfadine Sulfate, Triclozan, Octopyrox, Parachlorometa Xylenol, Nystatin, Tol Naphtate and clotrimazole.

Various alpha-hydroxy acids and beta-hydroxy acids may be useful for pharmacological and cosmetic purposes of the skin, such as anti-aging, reduced dryness, skin deprivation, and reduction of wrinkles and fine lines. This includes salicylic acid, glycolic acid and lactic acid.

Sunscreens are also useful herein. US Pat. No. 5,087,445 to Haffey et al. On Feb. 11, 1992, various sunscreens are incorporated herein by reference in their entirety; US Patent No. 5,073,372, issued to Turner et al. On December 17, 1991; US Patent No. 5,073,371 to Turner et al. On December 17, 1991; And in Segarin et al., Chapter VIII, beginning on page 189, Cosmetics Science and Technology. The sunscreen includes 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl N, N-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid, octocryl Ethylene, oxybenzone, homomentyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3- (4 -Methylbenzylidene) camphor, titanium dioxide, zinc dioxide, silica, iron oxide and mixtures thereof.

In general, sunscreen agents may comprise from about 0.5% to about 20% of compositions useful herein. The actual amount will vary depending on the sunscreen chosen and the desired Sun Protection Index (SPF). SPF is a commonly used measure of the photoprotective properties of sunscreens against erythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978, which is hereby incorporated by reference in its entirety.

Sunless tanning agents including dihydroxyacetone, glyceraldehyde, indole, derivatives thereof, and the like are also useful in the present invention. The sunless tanning agent may also be used with sunscreen.

Other useful active ingredients include skin bleach (or whitening agents), including but not limited to hydroquinone, ascorbic acid, kojic acid, and sodium metabisulfite.

Other useful active ingredients particularly useful in hair care compositions include anti-dandruff agents such as zinc pyrithione, octopyrox, selenium disulfide, sulfur, coal tar and the like.

In addition to antibacterial agents, zinc pyrithione and triclozan can be used in antiperspirants and deodorants for use under the body, especially under armpits.

conditioner for hair

The compositions of the present invention may include various conditioning agents for use on the hair or skin. Conditioning agents are typically used at from about 0.05% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 5% by weight of the composition. As used herein, nonvolatile has the meaning as defined above.

Conditioning agents useful herein, and especially conditioning agents useful in hair and skin care compositions, include non-volatile conditioning fluids such as hydrocarbons, silicone fluids, fatty esters and fatty alcohols, as well as cationic materials.

The conditioning fluid generally has a viscosity of about 3,000,000cs or less, preferably about 2,000,000cs or less, more preferably 1,500,000cs or less.

The conditioning fluid includes a liquid selected from the group consisting of hydrocarbon oils and fatty esters. Fatty esters are characterized by having at least 10 carbon atoms and include esters having hydrocarbyl chains derived from fatty acids or alcohols such as mono-esters, polyhydric alcohol esters and di- and tri-carboxylic acid esters. Hydrocarbyl radicals of the fatty esters herein may include or be covalently bonded to other miscible functional groups such as amides and alkoxy moieties (eg, ethoxy or ether bonds, etc.).

Hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), and branched chain aliphatic hydrocarbons (saturated or unsaturated). Straight chain hydrocarbon oils preferably contain about 12 to about 19 carbon atoms but the hydrocarbon need not necessarily be limited to the above range. Branched chain hydrocarbon oils may typically contain a greater number of carbon atoms. Also included herein are polymeric hydrocarbons of alkenyl monomers, such as C ₂ -C ₆ alkenyl monomers. Specific examples of suitable materials include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane and mixtures thereof. Preferred hydrocarbon polymers are polybutenes such as copolymers of isobutylene and butenes. A commercially available material of this type is L-14 polybutene from Amoco Chemical Co., Chicago, Illinois, USA.

The monocarboxylic acid esters herein include esters of alcohols and / or acids of the formula R'COOR, wherein the sum of the alkyl or alkenyl radicals and the carbon atoms in R and R 'is at least 10, preferably at least 20.

Fatty esters include, for example, alkyl and alkenyl esters of fatty acids having aliphatic chains having about 10 to about 22 carbon atoms, alkyl and / or alkenyl alcohol-derived aliphatic chains having about 10 to about 22 carbon atoms Alkyl and alkenyl fatty alcohol carboxylic esters and combinations thereof. For example isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostea Latex, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate and oleyl adipate to be. However, the mono-carboxylic acid ester does not need to contain at least one chain having at least 10 carbon atoms, as long as the number of aliphatic chain carbon atoms is at least 10. Examples are diisopropyl adipate, diisohexyl adipate and diisopropyl sebacate.

Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used. These include, for example, C ₄ -C ₈ dicarboxylic acids such as C ₁ -C ₂₂ (preferably C ₁ -C ₆ ) esters of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid and octanoic acid. Esters are included. Specific examples include isocetyl stearyl stearate, diisopropyl adipate and tristearyl citrate.

Polyhydric alcohol esters include alkylene glycol esters such as ethylene glycol mono and di-fatty acid esters, diethylene glycol mono- and di-fatty acid esters, polyethylene glycol mono- and di-fatty acid esters, propylene glycol mono- and di-fatty acid Esters, polypropylene glycol monooleate, polypropylene glycol 2000 monostearate, ethoxylated propylene glycol monostearate, glyceryl mono- and di-fatty acid esters, polyglycerol poly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butylene glycol monostearate, 1,3-butylene glycol distearate, polyoxyethylene polyol fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters are satisfactory for use herein. Polyhydric alcohol esters.

Glycerides include mono-, di- and tri-glycerides. More specifically mono-di- and tri-esters of glycerol and long chain carboxylic acids such as C ₁₀ -C ₂₂ carboxylic acids. Various materials of this type can be obtained from vegetable and animal fats and oils, such as castor oil, safflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin oil and soybean oil. Synthetic oils include triolein and tristearine glyceryl dilaurate. Preferred glycerides are di- and tri-glycerides. Triglycerides are particularly preferred.

Other conditioning agent fluids include fatty alcohols, preferably C ₁₀ -C ₂₂ alcohols such as stearyl and cetyl alcohol.

Other conditioning agents for hair and / or skin include urea; Guanidine; Aloe vera in any of its various forms (eg, aloe vera gel); Polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, butylene glycol, hexylene glycol and the like; Polyethylene glycol; Sugars and starches; Sugar and starch derivatives (eg alkoxylated glucose); Hyaluronic acid; Lactamide monoethanolamine; Acetamide monoethanolamine; And mixtures thereof.

Silicone Conditioning Agent

Optional components of the present invention are nonvolatile silicone conditioning agents.

Silicone conditioning agents suitable for use herein have an average viscosity of from about 1,000 to about 2,000,000 centistokes, more preferably from about 10,000 to about 1,800,000 centistokes, even more preferably from about 100,000 to about 1,500,000 centistokes at 25 ° C. The viscosity of the silicones herein can generally be measured by a glass capillary viscometer according to Dow Corning Corporate Test Method CTM0004 (July 20, 1970).

In the compositions herein, the silicone conditioning agent is typically from about 0.05% to about 10%, preferably from about 0.1% to about 10%, more preferably from about 0.5% to about 8%, most preferred by weight of the composition. Preferably from about 0.5% to about 5%.

Suitable insoluble nonvolatile silicone conditioning agents include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, and mixtures thereof. Other insoluble nonvolatile silicones may also be used. The silicone herein may be a silicone fluid or silicone gum. The term silicone fluid refers to a flowable silicone material having a viscosity of less than 1,000,000 centistokes at 25 ° C. Generally the viscosity of the fluid is from about 5 to 1,000,000 centistokes, preferably from about 10 to about 100,000 centistokes at 25 ° C. Silicon gum will be described in more detail next.

Silicone fluids herein include polyalkyl or polyaryl siloxanes having the formula:

Wherein R is alkyl or aryl and x is an integer from about 1 to about 8,000, preferably from about 5 to about 8,000. A represents a group blocking the ends of the silicone chains.

Alkyl or aryl groups substituted on the siloxane chain (R) or at the terminal (A) of the siloxane chain are non-irritating, nontoxic and otherwise when the resulting silicone is still fluid, hydrophobic and applied to the hair at room temperature. It may have any structure as long as it is not otherwise harmful, miscible with other components of the composition, stable under normal use and storage conditions, and can be deposited on the hair to condition the hair.

Suitable A groups include methyl, methoxy, ethoxy, propoxy and aryloxy. Two R groups on a silicon atom are the same or different groups. Preferably, the two R groups are the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Preferred silicones are polydimethyl siloxane, polydiethylsiloxane and polymethylphenylsiloxane. Polydimethylsiloxane is particularly preferred.

Non-volatile polyalkylsiloxane fluids usable herein may include, for example, polydimethylsiloxanes. Such siloxanes are, for example, the Viscasil ^R and SF 96 series from General Electric Company, and the Dow Corning 200 series from Dow Corning.

Polyalkylaryl siloxane fluids usable herein may include, for example, polymethylphenylsiloxanes. Such siloxanes are, for example, SF 1075 methyl phenyl fluid from General Electric Co. or 556 Cosetic Grade Fluid from Dow Corning.

Polyether siloxane copolymers that can be used include, for example, polypropylene oxide modified polydimethylsiloxanes (eg Dow Corning DC-1248), but ethylene oxide or mixtures of ethylene oxide and propylene oxide can also be used. The level of ethylene oxide and polypropylene oxide should be low enough to prevent dissolution in water and the composition.

Another silicone material that may be particularly useful in silicone conditioning agents is an insoluble silicone gum. The term silicone gum, as used herein, refers to polyorganosiloxane materials having a viscosity of at least 1,000,000 centistokes at 25 ° C. Silicone gums are described by Petrarch, and other US Pat. No. 4,152,416 to Spitzer et al., Dated May 1, 1979 and Noll, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Silicone gums are also described in General Electric Silicone Rubber Product Data Sheets SE30, SE 33, SE 54 and SE 76. All of these references are incorporated herein by reference. Silicone gums typically have a mass molecular weight of about 200,000, generally about 200,000 to about 1,000,000. Specific examples include polydimethylsiloxane (polydimethylsiloxane) (methylvinylsiloxane) copolymers, poly (dimethylsiloxane) (diphenylsiloxane) (methylvinylsiloxane) copolymers and mixtures thereof.

Cationic Polymer Hair Conditioning Agent

Compositions of the present invention may also include cationic polymer conditioning agents. The polymeric cationic conditioning agents herein generally range from about 0.05% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3% by weight of the shampoo composition. Used as The cationic conditioning polymer is preferably water soluble. A water soluble cationic organic polymer refers to a polymer that is sufficiently water soluble to form a substantially clear solution with the naked eye when the concentration in water (distilled water or its equivalent) at 25 ° C. is 0.1%. Preferably the polymer will be soluble enough to form a substantially clear solution when the concentration is 0.5% and more preferably when the concentration is 1.0%. Cationic polymers herein generally have a weight average molecular weight of at least about 5,000, typically from about 10,000 to about 10,000,000. Preferably, the molecular weight is about 100,000 to about 2,000,000. Cationic polymers are generally characterized as having cationic nitrogen-containing moieties such as quaternary ammonium or cationic amino moieties or mixtures thereof. Any anionic counterion for the cationic polymer can be used so long as it meets the water solubility conditions. Suitable counter ions are halides include, sulfate and methyl sulfate (e.g. Cl ^-, Br ^-, I ^- or F ^- preferably Cl ^-, Br ^{- -,} or I). The above list is not limiting and others may be used.

Cationic nitrogen-containing moieties will generally be present as substituents on some of the total monomer units of the cationic hair conditioning agent. Accordingly, cationic polymers may include copolymers of tertiary ammonium or cationic amine-substituted monomer units and other non-cationic units (hereinafter referred to as spacer monomer units), terpolymers, and the like. Such polymers are known in the art and various are disclosed in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, Estrin, Crosley and Haynes (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC, 1982). .

Suitable cationic polymers are, for example, acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylates, alkyl methacrylates, vinyl caprolactone and vinyl pyrrolidone Copolymers of water-soluble spacer monomers with vinyl monomers having cationic amine or quaternary ammonium functionality. The alkyl and dialkyl substituted monomers preferably have C ₁ -C ₇ alkyl groups, more preferably C ₁ -C ₃ alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohols (hydrolyzed by polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol.

Cationic amines may be primary, secondary or tertiary amines depending on the particular species and the pH of the shampoo. In general, secondary and tertiary amines, in particular tertiary amines, are preferred.

Amine-substituted vinyl monomers can be polymerized in amine form and optionally converted to ammonium by quaternization. The amines can also be quaternized similarly after polymer formation. For example, a salt of formula R'X wherein R 'is short-chain alkyl, preferably C ₁ -C ₇ alkyl, more preferably C ₁ -C ₃ alkyl, and X forms a water soluble salt with quaternary ammonium Quaternization).

Suitable cationic amino and quaternary ammonium monomers are, for example, dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, monoalkylaminoalkyl acrylates, monoalkylaminoalkyl methacrylates, trialkyl methacryloxyalkyl ammoniums Vinyl compounds substituted with salts, trialkyl acryloxyalkyl ammonium salts, diallyl quaternary ammonium salts, and vinyl quaternary ammonium monomers having cyclic cationic nitrogen-containing rings such as pyridium, imidazolium and quaternized pyrrolidone, Examples include alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone salts. The alkyl portion of the monomer is preferably lower alkyl, such as C ₁ -C ₃ alkyl, more preferably C ₁ -C ₂ alkyl.

Amine-substituted vinyl monomers suitable for use herein include dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates, dialkylaminoalkyl acrylamides and dialkylaminoalkyl methacrylamides, wherein the alkyl groups are preferably C ₁ -C ₇ hydrocarbyl, more preferably C ₁ -C ₃ alkyl).

Cationic polymers herein can include mixtures of monomer units derived from amine- and / or quaternary ammonium-substituted monomers and / or miscible spacer monomers.

Suitable cationic hair conditioning polymers include, for example, copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salts (e.g. hydrochloride) (in industry, CTFA (Cosmetic, Toiletry and Fragrance) Termed Polyquaternium-16), for example from BASF Wyandotte Corp. of Parsippany, NJ, under the trade name LUVIQUAT (e.g. Commercially available as Rubiquat FC 370; Copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (industrially referred to as polyquaternium-11 by CTFA), for example Gaf Corporation, Wayne, NJ Those sold under the trademark GAFQUAT from eg (GAFQUAT 755N); Cationic diallyl quaternary ammonium-containing polymers such as dimethyldiallylammonium chloride homopolymer and copolymers of acrylamide and dimethyldiallylammonium chloride (referred to as polyquaternium-6 and polyquaternium by CTFA, respectively) ); And inorganic acid salts of amino-alkyl esters of homo- and copolymers of unsaturated carboxylic acids with 3 to 5 carbon atoms as described in US Pat. No. 4,009,256, which is incorporated herein by reference.

Other cationic polymers that can be used include polysaccharide polymers such as cationic cellulose derivatives and cationic starch derivatives.

Suitable cationic polysaccharide polymers for use herein include those of the formula:

Wherein A is an anhydroglucose residue such as starch or cellulose anhydrous glucose residues; R is an alkylene oxyalkylene, polyoxyalkylene, hydroxyalkylene group or a combination thereof; R ¹ , R ² and R ³ are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl groups, where each group contains up to about 18 carbon atoms and the carbon atoms of each cationic moiety The total number of (ie, the sum of the carbon atoms in R ¹ , R ² , R ³ ) is preferably about 20 or less], and X is an anionic counterion as described above.

Cationic cellulose is commercially available as NJ elal (LR ^R) series of Armor Corporation call polymer (Polymer) Polymer JR ^R and from (Amerchol Corp.), Edison material, for example on the industry (CTFA) Polyquaternium-10 It is a salt of trimethyl ammonium substituted epoxide and hydroxyethyl cellulose called. Another type of cationic cellulose includes polymeric quaternary ammonium salts of hydroxyethyl cellulose and lauryl dimethyl ammonium-substituted epoxides, referred to in the industry (CTFA) polyquaternium 24. This material is commercially available from Amerkol Corporation under the tradename polymer LM-200.

Other cationic polymers that can be used include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride (commercially available as Jaguar ^R series from Celanese Corp.). Still other materials include nitrogen-containing cellulose ethers (such as those described in US Pat. No. 3,962,418, incorporated herein by reference) and copolymers of etherified cellulose and starch (eg, incorporated herein by reference. US Pat. No. 3,958,581).

Cationic Surfactant Conditioning Agent

Cationic surfactants useful herein as conditioning agents include quaternary ammonium salts or salts of fatty amines. Preferred quaternary ammonium salts are dialkyl dimethyl ammonium chlorides, wherein the alkyl group has 12 to 22 carbon atoms and is derived from long chain fatty acids. Representative quaternary ammonium salts include ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride and di (hydrogenated tallow) ammonium chloride. Other quaternary ammonium salts useful herein are didications such as tallow propane diammonium dichloride. Quaternary imidazolium salts are useful herein. Examples of such materials are imidazolium salts containing C ₁₂ -C ₂₂ alkyl groups, for example 1-methyl-1-[(stearoylamide) ethyl] -2-heptadecyl-4, 5-dihydroimime Dazolium chloride, 1-methyl-1-[(palmitoylamide) ethyl] -2-octadecyl-4,5-dihydroimidazolium chloride and 1-methyl-1-[(tallowamide) -ethyl] -2- tallow-imidazolium methyl sulfate. Salts of fatty amines are also useful herein. Examples of such compounds include stearylamine hydrochloride, soiamine hydrochloride and stearylamine formate. Useful conditioning agents are disclosed in US Pat. No. 4,387,090 to Bolich, issued June 7, 1983, which is incorporated herein by reference.

Cationic surfactant conditioning agents are generally used at levels of about 0.1% to about 5% by weight of the composition.

Surfactants

Surfactants are optional components of the compositions of the present invention. If present, the surfactant typically comprises from about 0.05% to about 50% of the composition. Surfactants are particularly useful in cleaning compositions such as shampoos and skin cleansing compositions and can be used for a variety of purposes in the above and other compositions herein. Examples of the use thereof are emulsifiers, solubilizers for other components, and conditioning (especially cationic surfactants). In the case of shampoos or other cleaning compositions, the level of surfactant is preferably from about 5% to about 30%, more preferably from 12% to about 25% of the composition. For conditioners, preferred levels of surfactant are from about 0.05% to about 5%. Surfactants useful in the compositions of the present invention include anionic, nonionic, cationic and amphoteric surfactants. US Pat. No. 5,151,209 to McCall et al., Sep. 29, 1992, which discloses various surfactants useful herein; US Patent No. 5,151,209, issued to Steuri et al. On September 29, 1992; And US Pat. No. 5,120,532, issued to Wells et al. On June 9, 1992.

Anionic detergents useful herein include alkyl and alkyl ether sulfates. The materials are typically of the formula ROSO ₃ M and RO (C ₂ H ₄ O) _X SO ₃ M, where R is alkyl or alkenyl having about 10 to about 20 carbon atoms, x is 1 to 10, M is a water soluble cation such as ammonium, sodium, potassium and triethanolamine).

Another suitable group of anionic surfactants is a formula R ₁ -SO ₃ -M wherein R ₁ is a straight or branched chain saturated aliphatic having from about 8 to about 24, preferably from about 12 to about 18 carbon atoms. Is a water-soluble salt of an organic sulfuric acid reaction product having a hydrocarbon radical, wherein M is a cation). Important examples include methane series hydrocarbons and sulfonating agents, including iso-, neo- and n-paraffins having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms, eg For example, SO ₃ , H ₂ SO ₄ , oleum are salts of organic sulfuric acid reaction products obtained by reacting according to known sulfonation methods including bleaching and hydrolysis. Alkali metal and ammonium sulfonated C ₁₂ -C ₁₈ n-paraffins are preferred.

Further examples of anionic surfactants falling within the scope of the present invention are reaction products of fatty acids neutralized with sodium hydroxide and esterified with isethionic acid, where fatty acids are derived from coconut oil and methyl tauride, for example. Sodium or potassium salts of fatty acid amides, wherein the fatty acids are derived from, for example, coconut oil. Still other various anionic synthetic surfactants are described in US Pat. No. 2,486,921; 2,486,922 and 2,396,278.

Still other anionic synthetic surfactants include the group represented by succinamate. These include disodium N-octadecylsulfosuccinamate; Tetrasodium N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate; Diamyl esters of sodium sulfosuccinic acid; Dihexyl ester of sodium sulfosuccinic acid; Surface active agents such as dioctyl esters of sodium sulfosuccinic acid.

Other anionic surfactants suitable for use herein are olefin sulfonates having about 12 to about 24 carbon atoms. An olefin surfactant is used herein to sulfonate an α-olefin with uncomplexed sulfur trioxide and then neutralize the acid reaction mixture to hydrolyze any sultone produced in the reaction to yield the corresponding hydroxy-alkanesulfonate. The compound which can be manufactured by this means. Α-olefins capable of producing olefin sulfonates are mono-olefins having from about 12 to about 24, preferably from about 14 to about 16 carbon atoms. Another group of anionic organic surfactants are β-alkyloxy alkanes sulfonates. This compound has the formula:

Wherein R ₁ is a straight alkyl group having from about 6 to about 20 carbon atoms, R ₂ is a lower alkyl group having from about 1 (preferably) to about 3 carbon atoms, and M is described herein. Water-soluble cations as shown.

Many additional non-soap synthetic anionic surfactants are described in McCutcheon's Detergents and Emulsifiers, 1984, Annual, published by Allured Publishing Corporation, which is incorporated herein by reference. . Many other anionic and other types of surfactants are also disclosed in US Pat. No. 3,929,678, issued to Laughlin et al. On Dec. 30, 1975, which is incorporated herein by reference. Soaps can also be used as anionic surfactants.

Nonionic surfactants can be defined in a broad sense as compounds obtainable by condensing alkylene oxide groups (originally hydrophilic) with organic hydrophobic compounds (which may be originally aliphatic or alkyl aromatic). Examples of nonionic surfactants are as follows:

1. derived from the condensation of ethylene oxide with a product obtained from the reaction of propylene oxide with an ethylene diamine product;

2. Condensation products of straight or branched chain aliphatic alcohols having about 8 to about 18 carbon atoms with ethylene oxide, for example coconut alcohol ethylene oxide having about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol Condensates, wherein the coconut alcohol moiety has from about 10 to about 14 carbon atoms;

3. Long chain tertiary amine oxides corresponding to the formula:

R ₁ R ₂ R ₃ N → O

Wherein R ₁ contains an alkyl, alkenyl or monohydroxy alkyl radical having from about 8 to about 18 carbon atoms, 0 to about 10 ethylene oxide residues and 0 to about 1 glyceryl residues, and R ₂ And R ₃ contains about 1 to about 3 carbon atoms and 0 to about 1 hydroxy group, for example a methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl radical (the arrow in the formula is semipolar Common indication of binding);

4. Long-chain tertiary phosphine oxides corresponding to the formula:

RR'RP → O

Wherein R contains an alkyl, alkenyl or monohydroxy alkyl radical having from about 8 to about 18 carbon atoms, 0 to about 10 ethylene oxide residues and 0 to about 1 glyceryl residues, R 'and R is an alkyl or monohydroxyalkyl group each containing from about 1 to about 3 carbon atoms (arrows in the formulas are common marks indicating semipolar bonds);

5. One short-chain alkyl or hydroxy alkyl radical (typically methyl) containing about 1 to about 3 carbon atoms and about 8 to about 20 carbon atoms and 0 to about 10 ethylene oxide residues and 0 Long chain dialkyl sulfoxides containing one long chain hydrophobic chain, such as alkyl, alkenyl, hydroxyalkyl or ketoalkyl radicals containing from about 1 glyceryl moiety, for example octadecyl methyl sulfoxide, 2-keto Tridecyl methyl sulfoxide, 3,6,9-trioxaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetradecyl methyl sulfoxide, 3-methoxy Tridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

6. N-polyhydroxy fatty acid amides, for example polyhydroxy having polyhydroxy functionality with three or more hydroxy groups, preferably derived from reducing sugars such as glucose, fructose, maltose, lactose and the like Hydrocarbyl C ₉ -C ₁₉ fatty acid amide. Surfactants of this type are disclosed in US Pat. No. 2,965,576 to E. Wilson, December 20, 1960, which is incorporated herein by reference.

Cationic surfactants, especially conditioner compositions, useful in the compositions of the present invention contain amino or quaternary ammonium hydrophilic moieties that are positively charged when dissolved in the aqueous compositions of the present invention. Cationic surfactants useful herein are described in M.C. Publishing Co., McCutcheon's Detergents Emulsifiers, (North American edition 1979); Schwartz et al., Surface Active Agent, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent No. 3,155,591 to Hilfer, issued November 3, 1964; U.S. Patent No. 3,929,678 to Raulin et al. On December 30, 1975; US Patent No. 3,959,461 to Bailey et al. On May 25, 1976; And US Patent No. 4,387,090 to Bolich Junier, dated June 7, 1983. When cationic surfactants are included in the compositions of the present invention, they are generally present from about 0.05% to about 5%.

Among the quaternary ammonium-containing cationic surfactants useful herein are those having the formula:

Wherein R ₁ to R ₄ are independently aliphatic groups having from about 1 to about 22 carbon atoms, or aromatic, alkoxy, polyoxyalkylene, alkylamido, hydrides having from about 12 to about 22 carbon atoms Oxyalkyl, aryl or alkylaryl groups; X is an anion selected from halogen, acetate, phosphate, nitrate and alkylsulfate radicals. Aliphatic groups may contain, in addition to carbon and hydrogen atoms, other groups such as ether bonds and amino groups. Longer chain aliphatic groups, for example groups having at least about 12 carbon atoms, may or may not be saturated.

Other quaternary ammonium salts useful herein are di-quaternary ammonium salts such as tallow propane diammonium dichloride.

Quaternary ammonium salts include dialkyldimethyl-ammonium chlorides, wherein the alkyl group has about 12 to about 22 carbon atoms and is derived from long chain fatty acids such as hydrogenated tallow fatty acids (tallow fatty acids are R ₁ and R ₂ is thereby mainly generating a quaternary compound having 16 to 18 carbon atoms). Examples of quaternary ammonium salts useful in the present invention include ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dietocoxyl Dimethyl Ammonium Chloride, Didocosyl Dimethyl Ammonium Chloride, Di (Hydrogenated Tallow) Dimethyl Ammonium Acetate, Dihexadecyl Dimethyl Ammonium Chloride, Dihexadecyl Dimethyl Ammonium Acetate, Ditallow Dipropyl Ammonium Phosphate, Ditallow Dimethyl Ammonium Nitrate, Di ( Coconutalkyl) dimethyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride. Ditallow dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and cetyl trimethyl ammonium chloride are preferred quaternary ammonium salts herein. Di- (saturated or unsaturated tallow) dimethyl ammonium chloride is a particularly preferred quaternary ammonium salt.

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactants. The alkyl group of such amines preferably has about 12 to about 22 carbon atoms and may be substituted or unsubstituted. Amines useful herein include stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soiamine, soyamine, myristyl amine, tridecylamine, ethyl stearylamine, N-tallowpropane diamine, Ethoxylated (5 molar EO) stearylamine, dihydroxy ethyl stearylamine and arachidylbehenylamine. Suitable amine salts include halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. Such salts include stearylamine hydrochloride, soiamine chloride, stearylamine formate, N-tallowpropane diamine dichloride and stearamidopropyl dimethylamine citrate. Cationic amine surfactants useful herein include those disclosed in US Pat. No. 4,275,055 to Nachtigal et al., June 23, 1981, incorporated herein by reference.

Amphoteric surfactants in the broad sense mean derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, wherein the aliphatic radicals are straight or branched and one of the aliphatic substituents contains about 8 to about 18 carbon atoms and the other One includes anionic accepting groups such as carboxy, sulfonate, sulfate, phosphate or phosphonate). The chemical formula of these compounds is as follows:

Wherein R ² contains an alkyl, alkenyl or hydroxy alkyl radical having from about 8 to about 18 carbon atoms, 0 to about 10 ethylene oxide residues and 0 to about 1 glyceryl residues; Y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R ³ is an alkyl or monohydroxyalkyl group containing from about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom and X is 2 when Y is a nitrogen or phosphorus atom; R ⁴ is alkylene or hydroxyalkylene having from about 1 to about 4 carbon atoms; Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphonate groups.

Other amphoteric substances such as betaine are also useful in the present invention. Examples of betaines useful herein include higher alkyl betaines such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis- (2-hydroxyethyl) carboxymethyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine and lauryl bis- (2-hydroxypropyl) alpha Carboxyethyl betaine. Representatives of sulfobetaines are coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis- (2-hydroxyethyl) sulfopropyl betaine, and amidobetaines. And amidosulfobetaine, wherein the RCONH (CH ₂ ) ₃ radical is bonded to the nitrogen atom of betaine is also useful in the present invention.

Other examples of amphoteric surfactants that may be used in the compositions of the present invention are derivatives of aliphatic secondary and tertiary amines in a broad sense, wherein the aliphatic radicals are straight or branched and one of the aliphatic substituents is from about 8 to about 18 Two carbon atoms and the other containing anionic accepting groups such as carboxy, sulfonate, sulfate, phosphate or phosphonate). Examples of compounds included within this definition are prepared by the reaction of sodium 3-dodecylaminopropionate, sodium 3-dodecylamino propane sulfonate, sodium isethionate and dodecylamine according to the teachings of US Pat. No. 2,658,072. N-alkyltaurine as described above, N-higher alkyl aspartic acid as taught in US Pat. No. 2,438,091, and a product such as that disclosed under US Pat. No. 2,528,378, commercially available.

Thickeners and suspending agents

The compositions of the present invention may include rheology modifiers such as various thickeners and / or suspending agents. Examples of this type of component are described below.

The composition may comprise a gel vehicle material. They are particularly useful for use in products such as hair rinses, creams and lotions.

The gel vehicle may comprise a liquid vehicle material and a cationic surfactant vehicle material as two essential components. Cationic surfactant materials are described in more detail below. Gel vehicles are generally described in Barry, The Self Bodying Action of the Mixed Emulsifier Sodium Dodecyl Sulfate / Cetyl Alcohol, 28 J, of Colloid and Interface Science 82-91 (1968); Barry et al., The Self-Bodying Action of Alkyltrimethylammonium Bromides / Ceostearyl Alcohol Mixed Emulsifiers; Influence of Quaternary Chain Length, 35 J, of Colloid and Interface Science 689-708 (1971); And Barry et al., Rheology of Systems Containing Cetomacrogol 1000-Cetostearyl Alcohol, I. Self-Bodying Action, 38 J, of Colloid and Interface Science 616-625 (1972).

Whether or not it contains a cationic surfactant, the carrier may have one or more liquid vehicle materials that are essentially water soluble and contain hydrophobic and hydrophilic moieties. Liquid vehicle materials include natural or synthetic acids, acid derivatives, alcohols, esters, ethers, ketones, and amides with chains of about 12 to about 22, preferably about 16 to about 18 carbons. . Fatty alcohols and fatty esters are preferred and fatty alcohols are particularly preferred.

Preferred esters for use herein include cetyl palmitate and glycerylmonostearate. Cetyl alcohol and stearyl alcohol are preferred alcohols. Particularly preferred liquid vehicle materials consist of a mixture of cetyl alcohol and stearyl alcohol, containing from about 55% to about 65% (by weight of the mixture) cetyl alcohol.

When the composition of the invention comprises a liquid vehicle material, the liquid vehicle material is present from about 0.1% to about 10.0% of the composition and the cationic surfactant vehicle material is present from about 0.05% to about 5.0% of the composition.

Nonionic cellulose ethers and water soluble gums may also be used to thicken the composition. For example, U.S. Patent No. issued to Glover on December 10, 1985, which teaches a hair conditioner comprising a suspension system consisting of glucan gum, guar gum and hydroxyethylcellulose, which is incorporated herein by reference. 4,557,928; And US Pat. No. 4,581,230 to Grollier et al. On April 8, 1986, which teaches a hair care cosmetic composition comprising a water soluble vegetable thickener such as hydroxyethylcellulose or guar gum as a thickener. Do it.

Cellulose ethers useful for preparing viscous compositions have a sufficient level of nonionic substituents to make the composition water soluble, selected from the group consisting of methyl, hydroxyethyl and hydroxypropyl, and are further from about 0.2% to less than 1% by weight. And those substituted with hydrocarbon radicals having from about 10 to about 24 carbon atoms in an amount that renders the cellulose ether of water soluble. The cellulose ether to be modified preferably has a low to medium molecular weight, ie less than about 800,000 and preferably about 20,000 to 700,000 (about 75 to 2500 D.P.).

Nonionic water soluble cellulose ethers are preferred polymers that can be used in hair care compositions. Commercially available nonionic cellulose ethers which are widely used include methyl cellulose, hydroxy propyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose.

Compositions of the present invention, in particular other thickeners for use in hair rinses, include combinations of hydrophobically-modified polymeric materials with surfactants, for example quaternary ammonium compounds (e.g. ditallowdimethyl ammonium chloride). Such vehicles include U.S. Patent Nos. 5,106,609, issued to Bolich et al. On April 21, 1992; U.S. Patent No. 5,100,658 to Bolich et al. On March 31, 1992; U.S. Patent No. 5,104,646 to Bolich et al. On April 14, 1992; US Pat. No. 5,100,657, issued March 31, 1992 to Ansher-Jackson et al. Hydrophobically modified nonionic water soluble polymer refers to a nonionic water soluble polymer modified by being substituted with an amount of hydrophobic groups sufficient to make the polymer less water soluble. By water soluble is meant that the polymer or salt constituting the polymer backbone of the thickener is sufficiently water soluble to form a substantially clear solution when dissolved in water at 25 ° C. by 1% based on the weight of the solution. Therefore, the polymer backbone of the main thickener may be essentially any water soluble polymer. The hydrophobic group can be a C ₈ -C ₂₂ alkyl, arylalkyl, alkylaryl group and mixtures thereof. The degree of hydrophobic substitution on the polymer backbone should be about 0.1% to about 1.0% depending on the particular polymer backbone. More generally, the ratio of hydrophilic portion to hydrophobic portion of the polymer is from about 10: 1 to about 1000: 1.

Preference is given to using nonionic water soluble cellulose ethers as polymer bases of hydrophobically modified polymers. Thus, for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, and methyl hydroxyethyl cellulose can be used.

It is contemplated to use suspending agents to thicken the composition or to suspend insoluble components of the composition. Suitable suspending agents are long chain acyl derivatives, long chain amine oxides and mixtures thereof, and such suspending agents are present in the shampoo composition in crystalline form. These various suspending agents are described in US Pat. No. 34,584, issued to Grote et al. On April 12, 1994. Ethylene glycol distearate is particularly preferred.

Among the long chain acyl derivatives useful as suspending agents are N, N-di (hydrogenated) C ₈ -C ₂₂ (preferably C ₁₂ -C ₂₂ , more preferably C ₁₆ -C ₁₈ ) amido benzoic acid, or soluble salts thereof (E.g., K, Na salts), in particular N, N-di (hydrogenated) tallow amido benzoic acid sold by Stepan Company, Northfield, Illinois.

Another component useful in the composition for thickening or suspending insoluble components is crosslinked carboxylic acid polymeric thickeners. This crosslinked polymer contains at least one monomer derived from acrylic acid, substituted acrylic acid, salts and esters of the acrylic acid and substituted acrylic acid, wherein the crosslinker contains at least two carbon-carbon double bonds and is derived from a polyhydric alcohol. do.

Examples of commercially available carboxylic acid polymers include carbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose or pentaerythritol. Carbomer is commercially available from BFGoodrich as the Carbopol ^R 900 series. Examples of commercially available copolymers include copolymers of acrylic acid, methacrylic acid or one or more short chain (ie, C ₁ -C ₄ alcohol) esters with C ₁₀ -C ₃₀ alkyl acrylates, wherein the crosslinker is sucrose Or allyl ether of pentaerythritol. The copolymer is known as an acrylate / C ₁₀ -C ₃₀ alkyl acrylate crosspolymer and is available from B.F. Goodrich from Carbopol 1342, Pemulen TR-1, and Pemulen TR. It is commercially available as -2.

When thickeners are used, the compositions of the present invention generally comprise from about 0.01% to about 2%, more preferably from about 0.05% to about 1% and most preferably from about 0.10% to about 0.75% of carboxylic acid polymer thickener. something to do.

Other thickeners include low pH thickeners, such as polyacrylamides available as Seppigel from Seppic Corporation; And crosslinked methyl quaternized dimethylaminomethacrylate commercially available from Allied Colloids as Salcare SC95.

Emulsifier

The compositions herein may contain various emulsifiers. Such emulsifiers are useful for emulsifying the various carrier components of the compositions of the present invention and are not necessary to dissolve or disperse the copolymers of the present invention. Suitable emulsifiers may include any of a variety of nonionic, cationic, anionic and zwitterionic surfactants as described above and described in the general literature. See, eg, McCutcheon's, Detergents and Emulsifiers, North American Edition (1986), published by Allure Publishing Publishing Corporation; US Patent No. 5,011,681 to Ciotti et al. On April 30, 1991; US Patent No. 4,421,769 to Dixon et al. On December 20, 1983; And U. S. Patent No. 3,755, 560 to Deckert et al. On August 28, 1973.

Suitable emulsifiers include esters of glycerin, esters of propylene glycol, fatty acid esters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters of sorbitan anhydride, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers, ethoxylates Silylated alcohols, alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyl lactylates, soaps and mixtures thereof.

Suitable emulsifiers are polyethylene glycol 20 sorbitan monolaurate (polysorbate 20), polyethylene glycol 5 soya sterol, steareth-20, ceeareth-20, PPG-2 methyl Glucose Ether Distearate, Ceteth-10, Polysorbate 80, Cetyl Phosphate, Potassium Cetyl Phosphate, Diethanolamine Cetyl Phosphate, Polysorbate 60, Glyceryl Stearate, PEG-100 Stearate Rates and mixtures thereof, including but not limited to. Emulsifiers can be used alone or as a mixture of two or more, from about 0.1% to about 10%, more preferably from about 1% to about 7%, and most preferably from about 1% to about 5 of the composition of the present invention. You can configure%.

Additional ingredients

The compositions herein may contain a variety of other optional ingredients suitable for making the composition aesthetically or aesthetically better to improve storage stability and efficacy or to confer additional use advantages. Such conventional optional ingredients are well known to those skilled in the art and include, for example, pigments and dyes, perfumes, pearlescent aids (eg ethylene glycol distearate), preservatives (eg benzyl) Alcohols, methyl parabens, propyl parabens and imidazolidinyl ureas, thickeners and viscosity modifiers (e.g., diethanolamides of long chain fatty acids (e.g. PEG 3 lauric diethanolamide), cocomonoethanolamide, guar gum, Methyl cellulose, starch and starch derivatives), fatty alcohols (e.g. cetearyl alcohol), sodium chloride, sodium sulfate, polyvinyl alcohol, ethyl alcohol, pH adjusting agents (e.g. citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, Sodium carbonate), salts (usually potassium acetate and sodium chloride), colorants (e.g. FDC or DG dyes), fragrances, metal ion sequestrants (disodium ethylene Amine tetra-acetate), polymeric plasticizers (e.g. glycerin, diisobutyl adipate, butyl stearate and propylene glycol), vitamins and derivatives thereof (e.g. ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol , Retinoids, etc.), skin sensates, astringents, skin sedatives, skin treatments, and the like, and non-limiting examples of aesthetic ingredients include panthenol and derivatives (e.g. ethyl panthenol), pantothenic acid and derivatives thereof, clove oil, menthol , Camphor, eucalyptus oil, eugenol, methyl lactate, witch hazel distillate, allantoin, bisbalol, dipotassium glycyrginate, and the like), compositions for assisting film formation and identity of the composition (E.g. copolymers of eicosene and vinyl pyrrolidone, e.g. from GAF Chemical Corporation) E. The Annex ^{V-220 (Garnex R V-} 220), preservatives, skin penetration aids for maintaining the generation of the compositions, wherein (a commercially available example DMSO, 1- dodecyl aza-cycloheptane-2-one (camphor eopjon Needle ( Commercially available as Azone from Upjohn Co.), and the like. These optional ingredients are generally present at levels of from about 0.01% to about 10.0%, preferably from about 0.05% to about 5.0%, respectively of the composition.

How to use a personal topical care composition

The compositions of the present invention provide a suitable benefit to the product, such as, for example, hair styling, fixation, cleansing, conditioning for hair care products and moisturizing, sun block, acne treatment, for skin care products, Used according to conventional methods to provide wrinkle removal, artificial sunbathing, analgesia and other cosmetic and pharmaceutical benefits. The method of use depends on the type of composition used, but generally an effective amount of the product is applied to the hair or skin and then rinsed off from the hair or skin (for shampoos and some conditioning products) or left on the hair (sprays). , Mousse or gel product) on the skin (for skin care compositions). By effective amount is meant an amount sufficient to provide the desired advantage. Preferably, the hair rinse, mousse and gel products are applied to wet or damp hair prior to drying and styling the hair. After applying the composition to the hair, the hair is dried and styled in the user's usual manner. Hair sprays are typically applied to hair that has already been dried and styled. Cosmetic and pharmaceutical topical skin care compositions are applied to the skin and rubbed.

The following examples further illustrate preferred embodiments within the scope of the present invention. The examples are given for illustrative purposes only and are not intended to limit the invention, and many modifications are possible without departing from the spirit and scope of the invention.

Experiment

Silicone macromers I and II and polymers I, II and III can be synthesized according to the following procedure. The production process can be modified in many ways at the sole discretion of the synthetic chemist (e.g., degassing method and gas selection, initiator type selection, conversion, reactant amount, etc.). The choice of initiator and solvent is often determined by the requirements of the particular monomer used, since different monomers have different solubility and different reactivity with respect to the particular initiator.

Synthesis of 1- (dimethylchlorosilyl) -2- (p-styryl) ethane end-cap

In a three neck round bottom flask equipped with a magnetic stirrer, thermometer and addition funnel, a solution of vinyl benzene (50.0 g, 0.384 mol) and chlorodimethyl silane (11.113 g, 0.128 mol) was dried with anhydrous tetrahydrofuran (THF) (200 ml). It is prepared in. To the solution is added dropwise a chloroplatinic acid solution (0.150 g in 20 mL THF). Since the reaction is very exothermic, it is necessary to add chloroplatinic acid slowly. After the addition of the platinum acid, the reaction proceeds with stirring for an additional hour. Using this solution (10.64M), styrene end-capped silicone macromer I is prepared as described below.

Silicone Macromers I and II

In a round bottom flask equipped with a magnetic stirrer, a solution of hexamethylcyclotrisiloxane monomer (150 g) is prepared in anhydrous cyclohexane (150 g). Secondary-butyl lithium (0.0125 moles) initiator is added dropwise. The reaction mixture is stirred for 10 minutes. After this step, THF (150 g) is added to the reaction mixture. The solution is stirred overnight and then heated at 50 ° C. for 5 hours. End-cap (0.025 mol) is then slowly added to the solution. Silicone macromer I is prepared with 1- (dimethylchlorosilyl) -2- (p-styryl) ethane end-cap, prepared previously. The end-cap synthesis solution of the end-cap synthesis process is added dropwise. Silicone macromers II are described by Holohan, George, Barrie and Parker, Monofunctional Polydimethylsiloxane Oligomers For Graft Copolymerization, Macromol. Chem. Phys. 195, 2965-2979 (1994), are prepared as chlorodimethylstyrylsilane end-caps, which may be prepared as described and presented. The end-cap obtained from the synthesis process is added dropwise to the solution. On the one hand the end-cap is dissolved in THF and then added dropwise. The macromer is recovered by precipitating the final solution in methanol.

Polymer I

Into the flask is placed 20 parts acrylic acid, 63 parts t-butylacrylate and 17 parts styrene end-capped polydimethylsiloxane macromer (silicone macromer I). Sufficient ethyl acetate or acetone (preferably acetone) is added as reaction solvent to bring the final monomer concentration to 25%. The initiator azobisisobutyronitrile is added to a level of 0.5% by weight relative to the amount of monomer. Oxygen is purged from the flask by inserting an argon gas line below the liquid surface to foam argon into the reaction solvent for about 15 minutes. The temperature is maintained for 48 hours while heating to 60 ° C. and shaking. The reaction was terminated by cooling to room temperature and the reaction mixture was poured into a teflon-coated pan and placed in a vacuum oven to dry remove the reaction solvent.

Polymer II

20 parts acrylic acid, 63 parts t-butylacrylate and 17 parts styrene end-capped polydimethylsiloxane macromer (silicone macromer II) are placed in the flask. Sufficient ethyl acetate or acetone (preferably acetone) is added as reaction solvent to bring the final monomer concentration to 25%. The initiator azobisisobutyronitrile is added to a level of 0.5% by weight relative to the amount of monomer. Oxygen is purged from the flask by inserting an argon gas line below the liquid surface to foam argon into the reaction solvent for about 15 minutes. The temperature is maintained for 48 hours while heating to 60 ° C. and shaking. The reaction was terminated by cooling to room temperature and the reaction mixture was poured into a teflon-coated pan and placed in a vacuum oven to dry remove the reaction solvent.

Polymer III

Into the flask is placed 20 parts acrylic acid, 30 parts N-isopropylacrylamide, 35 parts t-butylacrylate and 15 parts styrene end-capped polydimethylsiloxane macromer (silicone macromer I). Sufficient ethyl acetate or acetone (preferably acetone) is added as reaction solvent to bring the final monomer concentration to 25%. The initiator azobisisobutyronitrile is added to a level of 0.5% by weight relative to the amount of monomer. Oxygen is purged from the flask by inserting an argon gas line below the liquid surface to foam argon into the reaction solvent for about 15 minutes. The temperature is maintained for 48 hours while heating to 60 ° C. and shaking. The reaction was terminated by cooling to room temperature and the reaction mixture was poured into a teflon-coated pan and placed in a vacuum oven to dry remove the reaction solvent.

Example

The following examples further illustrate the invention and illustrate embodiments that fall within the scope of the invention. The examples are given for illustrative purposes only and are not intended to limit the invention, and many modifications are possible without departing from the spirit and scope of the invention. Unless otherwise stated, ethanol is anhydrous in the following formulations.

Examples 1-4

Examples of mousse compositions of the invention are described below:

Ingredient (% by weight) One 2 3 4 Polymer III 3.00 3.00 3.00 3.00 Lauramin-oxide 0.10 0.10 0.00 0.10 Cocoamidopropyl betaine 1.33 1.33 0.30 1.33 Propylene glycol 0.20 0.10 0.10 0.10 Spices 0.10 0.10 0.05 0.10 Disodium EDTA-Dihydrate 0.10 0.10 0.10 0.10 Phenoxyethanol 0.25 0.25 0.25 0.25 Methyl paraben 0.15 0.15 0.15 0.15 Polyquaternium-4 ¹ 0.00 0.00 0.00 0.20 Stearyltrimethylammonium Chloride 0.00 0.00 0.20 0.00 KOH solution (45% active) 0.80 0.80 1.00 0.90 Deionized water Enough Enough Enough Enough ¹ Celquat L200, National Starch and Chemical Corp., Bridgewater, NJ, Copolymer of hydroxyethylcellulose and diallyldimethyl ammonium chloride

After mixing the aqueous solution of the silicone grafted copolymer with the aqueous KOH solution, the remaining ingredients except the fragrance are added with stirring, heated to 40 to 60 ℃ with stirring, and the composition is cooled to room temperature with stirring for about 8 hours. After mixing, mix with spices. The product is then filled into a conventional aerosol or aerosol mousse spray container.

Examples 5-8

Some examples of reduced VOC hair spray compositions of the present invention are described below:

Ingredient (% by weight) 5 6 7 8 Polymer I or II 4.50 3.50 4.00 3.00 Deionized water 5.00 3.00 18.00 17.00 Isododeccan 1.50 0.00 0.00 0.00 KOH solution (45% active) 0.90 0.65 0.00 0.75 NaOH solution (30% active) 0.00 0.00 1.00 0.00 Triethyl citrate 0.20 0.40 0.00 0.10 Spices 0.10 0.25 0.05 0.10 Propylene glycol 0.05 0.00 0.00 0.10 N-butane (propellant) 7.50 6.00 0.00 0.00 HFC 152A (Propellant) 15.00 17.00 0.00 0.00 Dibutyl adipate 0.00 0.00 0.30 0.00 SDA 40 Ethanol Enough Enough Enough Enough

Ethanol is first added to the mixing vessel, then the remaining non-propellant components are added in the order shown above and vigorously stirred for 2-3 hours to prepare the composition. The compositions of Examples 5 and 6 are then added to conventional aerosol cans in a conventional manner and filled with propellant. The composition of the examples is added to a conventional non-aerosol pump spray container.

Example 9

Representative examples of shampoo compositions of the present invention are as follows:

ingredient weight% Ammonium Laureth Sulfate 5.00 Coco Amido Profile Betaine 6.00 Polymer III 4.00 NaOH solution (30% active) 0.10 PEG 150 distearate 2.00 Glidant ¹ 0.38 Aminomethylpropanol 0.40 Spices 1.00 Deionized water Enough ¹ Preservatives marketed from Glyco, Inc.

Ammonium laureth sulfate and silicone grafted copolymer (polymer III) are mixed and heated to 70 ° C. for about 30 minutes with mixing to prepare a shampoo. Add the remaining ingredients and mix for an additional 30 minutes. Then cooled to room temperature. If necessary, adjust the pH to 6.5 by adding citric acid or sodium hydroxide.

Example 10

Representative styling and conditioning hair rinse compositions of the present invention are as follows:

ingredient weight% Polymer III 3.00 NaOH solution (30% active) 0.90 Silicone premix Silicone Sword GE SE76 ¹ 0.50 Decamethyl cyclopentasiloxane 4.00 Main mixture Cetyl hydroxyethylcellulose ² 0.60 Locust bean sword 0.50 EDTA, disodium salt 0.15 DTDMAC 0.65 Glidant ³ 0.40 Deionized water Enough ¹ Commercially available from General Electric ² Polysurf ³ commercially available from Aqualon Co. ³ Preservatives commercially available from Glyco Incorporated

The silicone premixes are mixed separately by conventional methods. All ingredients are added and heated to 95 ° C. for 30 minutes with shaking, to prepare the main mixture. Cool to about 60 ° C., add the silicone premix, silicone grafted copolymer (polymer III) and NaOH solution to the main mixture with shaking and cool to room temperature.

Example 11

A reduced VOC hair spray composition is prepared from the following ingredients:

ingredient A B C D water Volume to become 100 Volume to become 100 Volume to become 100 Volume to become 100 ethanol 54.0 54.0 54.0 54.0 Polymer I, II or III 4.0 3.0 4.0 3.0 KOH solution (45% active) 0.80 0.60 1.00 0.75 Dioctyl phthalate 0.40 - 0.10 - air freshener 0.05 0.2 - -

The products are prepared by first dissolving the polymer in ethanol with stirring. Then the remaining ingredients are added with stirring. The resulting hair spray composition can be filled in a non-aerosol spray pump. Alternatively, the composition is mixed with a conventional propellant and filled into an aerosol spray container.

Example 12

A mousse composition is prepared from the following ingredients using conventional mixing methods:

ingredient weight% A B C water Volume to become 100 Volume to become 100 Volume to become 100 Polymer III 3.00 2.50 3.50 NaOH solution (30% active) 0.80 0.50 0.90 Lauramid DEA 0.33 0.33 0.33 Sodium methyl oleyl taurate 1.67 1.67 1.67 DMDM Hydantoin 0.78 0.78 0.78 Disodium EDTA 0.20 0.20 0.20 Polyoxyalkylated Isostearyl Alcohol ¹ 0.10 0.10 0.10 air freshener 0.10 0.10 0.10 Propellant ² 7.0 7.0 7.0 ¹ Aerosurf 66-E10 ² Commercially available as a mixture of, for example, Propelant A46, 82.46% isobutane, 16.57% propane and 0.001% butane

The product is first prepared by dissolving the polymer in water with stirring. The remaining ingredients except the propellant are added with stirring. The resulting mousse concentrate is mixed with a conventional propellant (for example propelant A46) and filled with an aerosol spray. Mousses are useful for applying to hair to provide styling and fixation.

Example 13

Hair tonic compositions are prepared from the following ingredients using conventional mixing methods:

ingredient weight% A B C Ethanol (190 degrees) Volume to become 100 Volume to become 100 Volume to become 100 Polymer I, II or III 0.75 1.00 1.25 Aminomethyl propanol 0.15 0.18 0.22 air freshener 0.10 0.20 0.30

The products are prepared by first dissolving the polymer in ethanol with stirring and then adding flavoring and optional pigments. This hair tonic product is useful for applying to hair to provide styling and fixation properties.

Example 14

Conditioning and styling shampoo compositions are prepared from the following ingredients using conventional mixing methods:

ingredient weight% Styling agent Polymer III 3.00 NaOH solution (30% active) 0.20 Premix Silicone sword 0.50 Dimethicone, 350cs Fluid 0.50 Main mixture water Volume to become 100 Ammonium Lauryl Sulfate 11.00 Cocoamide MEA 2.00 Ethylene Glycol Distearate 1.00 Xanthan gum 1.20 Methylchloroisothiazolinone (and) methylisothiazolinone 0.04 Adjust the pH to 4.5 by adding citric acid as needed

First, xanthan gum is dissolved in water by a conventional mixing method to prepare a main mixture. The remaining main mixture components are added and heated to 150 ° F. for 30 minutes with shaking the main mixture. The styling agent and the premix are added every 10 minutes with shaking and the whole mixture is stirred while cooling to room temperature. The styling agent and the premix can be added at different time points using either high shear mixing or conventional shaking means, or only one of them, to obtain various particle diameters.

Example 15

Acne Treatment Composition

Acne treatment compositions are prepared by mixing the following ingredients using conventional mixing methods:

ingredient weight% water Volume to become 100 Salicylic acid 2.00 Polymer I, II or III 2.00 Ethanol (SDA 40) 40.00 Aminomethyl propanol 0.40

Example 16

Topical analgesic compositions are prepared by mixing the following ingredients using conventional mixing methods:

ingredient weight% Purified water Volume to become 100 Ibuprofen 2.00 Polymer III 2.00 Aminomethyl propanol 0.45 Ethanol (SDA 40) 20.00

Example 17

The composition for sunless tanning is prepared by mixing the following ingredients using conventional mixing methods:

ingredient weight% Phase A water Volume to become 100 Polymer III 2.00 NaOH solution (30% active) 0.70 Carbomer 934 ¹ 0.20 Carbomer 980 ² 0.15 Acrylic Acid Copolymer ³ 0.15 Phase B PPG-20 Methyl Glucose Ether Distearate 2.00 Tocopheryl acetate 1.20 Mineral oil 2.00 Stearyl alcohol 1.00 SeAH Butter 1.00 Cetyl alcohol 1.00 Seteareth-20 2.50 Shereth-2 1.00 Ceretsu-10 1.00 Phase C DEA-cetyl phosphate 0.75 Phase D Dihydroxyacetone 3.00 Phase E Butylene Glycol 2.00 DMDM Hydantoin (and) Iodopropynyl Butyl Carbamate 0.25 Phase F air freshener 1.00 Cyclomethicone 2.00 ¹ Commercially available from C. Goodrich as Carbopol 934 ² Commercially available from B.F. Goodrich as Carbopol 980 ³ Commercially available from B.F. Goodrich as Pemulen TRI

In a suitable vessel the components of phase A are dispersed in water and heated to 75-85 ° C. In a separate vessel the components of phase B are combined and heated to 85-90 ° C. until they melt. DEA-cetyl phosphate is then added to liquid phase B and stirred until dissolved. The mixture is then added to phase A to form an emulsion. The emulsion is cooled to 40-45 ° C. with continued stirring. In a separate vessel, dihydroxyacetone is then dissolved in water and the resulting solution is mixed with the emulsion. In another vessel, the ingredients of phase E are mixed and heated to 40-45 ° C. until a clear solution is formed and the solution is added to the emulsion. Finally, the ingredients of phase F are added to the emulsion with mixing, cooled to 30-35 ° C. and then cooled to room temperature. Emulsions are useful for applying to the skin to provide an artificial sunbathing effect.

Example 18

Sunscreen composition

Oil-in-water emulsions are prepared by mixing the following ingredients using conventional mixing methods:

ingredient weight% Phase A water Volume to become 100 Carbomer 954 ¹ 0.24 Carbomer 1342 ² 0.16 Polymer III 1.75 NaOH (30%) 0.70 Disodium EDTA 0.05 Phase B Isoarakidil Neopentanoate ³ 2.00 PVP Eicosin Copolymer ⁴ 2.00 Octyl methoxycinnamate 7.50 Octocrylene 4.00 Oxybenzone 1.00 Titanium dioxide 2.00 Cetyl palmitate 0.75 Stearoxytrimethylsilane (and) Stearyl Alcohol ⁵ 0.50 Glyceryl Tribehenate ⁶ 0.75 Dimethicone 1.00 Tocopheryl acetate 0.10 DEA-cetyl phosphate 0.20 Phase C water 2.00 Triethanolamine 99% 0.60 Phase D water 2.00 Butylene Glycol 2.00 DMDM Hydantoin (and) Iodopropynyl Butyl Carbamate ⁷ 0.25 dL panthenol 1.00 Phase E Cyclomethicone 1.00 ¹ Commercially available as Carbopol 954 from B. Goodrich. ² Commercially available as Carbopol 1342 from B.F. Goodrich. ³ Commercially available as Elefac I-205 from Bernel Chemical. ⁴ Commercially available as GAnex V-220 from GAF Corporation. ⁵ Commercially available as DC 580 Wax from Dow Corning. ⁶ Synchrowax from Croda. commercially available as HRC) ⁷ from Lonza (Lonza) as a commercially available glycidyl danteu plus (Glydant Plus)

In a suitable vessel the components of phase A are dispersed in water and heated to 75-85 ° C. In a separate vessel the components of phase B (except DEA-cetyl phosphate) are combined and heated to 85-90 ° C. until melted. DEA-cetyl phosphate is then added to liquid phase B and stirred until dissolved. The mixture is then added to phase A to form an emulsion. The components of phase C are combined until dissolved and added to the emulsion. The emulsion is then cooled to 40-45 ° C. with continued stirring. In a separate vessel, the components of phase D are mixed and heated to 40-45 ° C. until a clear solution is formed and the solution is added to the emulsion. Finally, the emulsion is cooled to 35 ° C. and the ingredients of phase E are added and mixed. Emulsions are applied to the skin and are useful for protecting the skin from the harmful effects of ultraviolet radiation.

Example 19

Facial moisturizer

Residual facial emulsions are prepared by mixing the following ingredients using conventional mixing methods:

ingredient weight% water Volume to become 100 Polymer III 1.00 NaOH solution (30% active) 0.40 glycerin 3.00 Cetyl palmitate 3.00 Cetyl alcohol 1.26 Quaternium-22 1.00 Glyceryl Monohydroxy Stearate 0.74 Dimethicone 0.60 Stearic acid 0.55 Octyldodecyl Myristate 0.20 Carbomer 1342 0.125 Tetrasodium EDTA 0.10 DMDM Hydantoin and Iodopropynyl Butyl Carbamate 0.10 Carbomer 951 0.075

Claims (10)

(a) (i) 1% to 99% acid-containing monomer based on the weight of the silicone grafted copolymer; (ii) 1% to 50% of styrene end-capped silicone macromers (Formula 1) or alkenyl end-capped silicone macromers (Formula 2) or combinations thereof based on the weight of the silicone grafted copolymer ; (iii) 0.1% to 50%, based on the weight of the composition, of the silicone grafted copolymer containing 0% to 98% of additional monomers and combinations thereof, based on the weight of the silicone grafted copolymer; And (b) from 1% to 99.9% (by weight of the composition) of an aqueous or hydroalcoholic solvent for dissolving or dispersing the copolymer and suitable for silicone grafted copolymers suitable for application to hair or skin, A personal topical care composition suitable for topical application to skin or hair and containing a silicone grafted copolymer having improved resistance to hydrolysis: Formula 1 Formula 2 In the above formula, s is an integer from 0 to 6; m is an integer from 1 to 3; R ² is C ₁ -C ₁₀ alkyl or C ₇ -C ₁₀ alkylaryl; n is an integer from 0 to 4; X is a chemical formula An ethylenically unsaturated group of wherein R ³ is H or C ₁ -C ₆ alkyl and R ⁴ is H or C ₁ -C ₆ alkyl; Z is a chemical formula Wherein each R ¹ is independently alkyl, aryl or alkylaryl having 1 to 10 carbon atoms, and r is an integer from 4 to 700. The method of claim 1, The silicone macromer is a styrene end-capped silicone macromer, n is 0, and the-(CH ₂ ) _S -Si (R ¹ ) _3-m -Z _m of the silicone macromer, where s is 0 to 2 M is 1, R ³ is H, R ⁴ is H or CH ₃ , R ¹ is alkyl and preferably R is methyl and r is from 50 to 500) Composition. The method according to claim 1 or 2, The copolymer comprises from 1% to 50% additional monomer by weight of the copolymer, the additional monomer being nonionic, cationic, amphoteric or a combination thereof, preferably the additional monomer is Acrylic and methacrylic acid esters of C ₁ -C ₂₄ alcohols; Styrene; Alkyl styrene; Chlorostyrene; Vinyl esters; Vinyl chloride; Vinyl toluene; Vinyl caprolactam; Vinylidene chloride; Acrylonitrile; Alpha-alkylstyrene; 1,3-dialkene; Ethylenically monounsaturated hydrocarbons; Alkoxyalkyl (meth) acrylates; Alkyl vinyl ethers; Di-acrylates and di-methacrylates; Acrylamide; Methacrylamide; Diacetone acrylamide; N, N-dialkyl (meth) acrylamide; N-alkyl (meth) acrylamides; Acrylate and methacrylate alcohols; Vinyl pyrrolidone; Allyl alcohol; Vinyl alcohol; And a nonionic monomer selected from the group consisting of a combination thereof. The method according to any one of claims 1 to 3, Wherein said acid-containing monomer is selected from the group consisting of carboxylic acid and sulfonic acid. The method according to any one of claims 1 to 4, Wherein said acid-containing monomer is a carboxylic acid. The method according to any one of claims 1 to 5, Wherein said carboxylic acid monomer is selected from the group consisting of monomers corresponding to the formula: Wherein R ⁵ and R ⁶ are independently H or C ₁ -C ₆ alkyl; R ⁷ is H, C ₁ -C ₆ alkyl or a carboxylic acid residue having up to 12 carbon atoms; R ⁸ is a carboxylic acid residue having up to 12 carbon atoms. The method according to any one of claims 1 to 6, The copolymer comprises (i) from 5% to 90% of said acid-containing monomer by weight of the copolymer; (ii) 2% to 40% of said silicone macromers; (iii) 0% to 70% of said additional monomer. The method according to any one of claims 1 to 7, Wherein said copolymer comprises (i) from 10% to 75% of said acid-containing monomer by weight of the copolymer; (ii) 5% to 40% of the silicone macromer; (iii) 5% to 70% of said additional monomer. The method according to any one of claims 1 to 8, Wherein said copolymer comprises (i) 15% to 50% of said acid-containing monomer by weight of the copolymer; (ii) from 5% to 25% of said silicone monomers; (iii) 40% to 70% of said additional monomer. A hair spray product comprising the composition of any one of claims 1 to 9 in an aerosol or non-aerosol spray container.