EP1139981A2

EP1139981A2 - Compositions and methods of using the same

Info

Publication number: EP1139981A2
Application number: EP99968903A
Authority: EP
Inventors: Andrew M. Homola; Ronald K. Dunton; Gary Pitts
Original assignee: Four Star Partners
Current assignee: Four Star Partners
Priority date: 1998-12-24
Filing date: 1999-12-23
Publication date: 2001-10-10
Also published as: EP1139981A4; CA2356840A1; WO2000038617A3; WO2000038617A2; AU2710300A

Abstract

The present invention discloses compositions containing a one or more transfer agents and one or more barrier materials which form, upon application to a substrate, even a wet substrate or substrate immersed under water, adhesive, protective barriers. The compositions may be modified to provide an appropriate viscosity and other characteristics and may serve as a carrier for active agents.

Description

TITLE OF THE INVENTION

COMPOSITIONS AND METHODS OF USING THE SAME

This application claims priority to U.S. Provisional Application Serial Nos.

60/113,950, filed December 24, 1998, and 60/117,283, filed January 26, 1999.

BACKGROUND OF THE INVENTION

Field of the Invention:

The present invention relates to compositions and methods of using the same.

In particular, the present invention relates to novel protective compositions and

methods of treating certain surfaces. In a preferred embodiment, the present invention

relates to skin care and specifically to methods of treating the skin, even wet skin or

skin which is immersed in water, with compositions, which provide the skin with a

protective barrier. The present invention also relates to compositions which provide

the skin, even wet skin or skin which is immersed in water, with a protective barrier.

The present invention also relates to compositions which can clean and remove

contamination from the skin while applying a protective barrier. Throughout this

invention, the term "skin" is meant to include not only the exterior integument or

dermis/epidermis/stratum corneum of man but also the internal and external surfaces

of organs and vessels including wounds, linings, membranous surfaces and glomeruli

of man and other animals, and other surfaces such as glass, metal, paint, plastic, and

all others which, like skin, can be electrostatically negatively charged. Discussion of the Background:

Numerous types of skin care compositions are known. For example, skin care

compositions are often classified as being either medicated or non-medicated. Other

types of skin care compositions include, e.g., sun blockers, moisturizers, etc.

However, two general drawbacks of many skin care compositions are that they are

difficult or impossible to apply to wet (or sweaty) skin and they are easily removed

from the skin. Thus, one goal of the present invention is to provide skin care

compositions which provide a long-lasting, protective barrier on the skin. Another

goal of this invention is to provide skin care compositions which can effectively and

aesthetically be applied to skin which is wet or even immersed under water or aqueous

solutions. Yet another goal of this invention is to provide skin care compositions

which can effectively and aesthetically be applied to skin to clean and remove

contaminants from skin which is wet or even immersed under water or aqueous

solutions.

SUMMARY OF THE INVENTION

Accordingly, it is one object of the present invention to provide novel skin

care compositions.

It is another object of the present invention to provide novel skin care

compositions which provide a long-lasting protective barrier on the skin.

It is another object of the present invention to provide a method for treating the

skin which confers improved protection to the skin. It is another object of the present invention to provide novel skin care

compositions which can be effectively and aesthetically applied to skin which is wet

or even immersed under water or aqueous solutions.

It is another object of the present invention to provide novel skin care

compositions which can effectively and aesthetically be applied to skin to clean and

remove contaminants from skin which is wet or even immersed under water or

aqueous solutions.

These and other objects, which will become apparent during the following

detailed description, have been achieved by the inventors' discovery that application

of a composition which comprises:

(a) 0.25 to 25 wt.%, based on the total weight of (a) and (b), of one or more

transfer agents; and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of one or more

barrier materials,

to the skin results in the formation of a protective barrier on the skin.

The inventors have also discovered that compositions which comprise:

(a') 65 to 99.75 wt.%, based on the total weight of (a') and (b'), of one or more

barrier materials; and

(b') 0.25 to 35 wt.%, based on the total weight of (a') and (b'), of a mixture,

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and (b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b"'), of

one or more skin care agents,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%, based on the total weight of said composition,

are useful for applying the skin care agent to the skin.

The inventors have also discovered that compositions comprising:

(1) 25 to 80 wt.%, based on the total weight of (1), (2), and (3), of a barrier

material;

(2) 1 to 50 wt.%, based on the total weight of (1), (2), and (3), of lecithin; and

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water,

are useful for applying the skin care agent to the skin.

The inventors have also discovered that compositions comprising:

(i) 1 to 30 wt.%), based on the total weight of (i), (ii), and (iii), of lecithin;

(ii) 10 to 30 wt.%), based on the total weight of (i), (ii), and (iii), of a barrier

material; and

(iii) 1 to 50 wt.%), based on the total weight of (i), (ii), and (iii), of chitosan,

are useful as skin care formulations.

Thus, the present invention provides new compositions which form long-

lasting, protective barriers on the skin and can be effectively and aesthetically applied

to wet or dry skin, skin which is covered with sweat or other secretions, skin which is

soiled or contaminated or skin which is immersed under water or aqueous solutions.

The methods of this invention result in the electrostatic bonding of waxy materials to

the skin. The compositions of the present invention may be applied to the skin either by

hand or by using any of a variety of skin application appliances, such as an atomizer,

spray can, brush, wipe, cotton puff, roll-on device, or other system or device

particularly applicable to the specific surface being treated.

The materials used for covering the applicator-ends of the appliance may

include, for example: a) natural or synthetic yarn, filaments, or other fibrous material

either as such or assembled as a textile, or to any braided, stranded, woven,

non- woven, knitted, matted, felted, etc. material, in which the materials of the

composition of the present invention (hereinafter MCPI) are held among or between

the fibers or the strands of the materials; b) foam-like or otherwise porous materials in

which the MCPI are held within pores or apertures; or c) non-porous, non-fibrous

materials such as some types of wood, plastic, metal, etc.

Thus, in one embodiment of the present invention, a single monolayer is

composed of a low molecular weight transfer agent in which positively charged

groups react with the negatively charged surfaces of the skin and the water repelling

part of the hydrophobic chain forms a highly hydrophobic interface. Examples of

such transfer agents are cetyltrimethylammonium bromide (CTAB),

hexadecyltrimethylammonium bromide (HDTAB), 5-amino-l,3-bis(2-ethylhexyl)-5-

methylhexahydro-5-methylpyrimidine (hexetidine) and various amines and quaternary

amines, of which a good example is Hyamine-1622 quaternary amine.

The compositions of the present invention are generally liquid, semi-solid or

solid state materials which may be applied to skin surfaces by hand, by pouring, by

injection, or by flowing. For the compositions of the present invention to be applied through the use of an atomizer, spray can, brush, wipe, cotton puff, roll-on device, or

any other applicator or method of application by which liquid, semi-solid, or solid

materials may be brought into contact with the skin, it may be necessary to modify the

viscosity of the composition with suitable volatile solvents known in the art or to form

emulsions by known means to provide formulations of appropriate viscosities.

The compositions of the present invention, as applied to the skin, provide a

multi-component protective coating (hereafter called the "Protective Coating: or

"PC"), as follows:

(1) The transfer agent component has dual functionality, being composed of

materials having some molecular segments or parts of a polymeric chain which are

positively charged and other such segments which exhibit hydrophobic characteristics.

(2) The barrier component is a hydrophobic, inert material (hereafter called

the "barrier" material), such as a wax or polydimethylsiloxane which mixes with and

adheres to the relatively uncharged, hydrophobic molecular segments or parts of the

transfer agent molecule. The thickness of the barrier stratum is typically between

about 1 and about 10 microns but can be thinner or thicker depending on the

requirements of the particular application.

(3) Compositions of the present invention may optionally include one or more

active agents which are intended to provide specific medical, cosmetic, or other

effects according to the known art relating to such ingredients. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Thus, in a first embodiment, the present invention provides novel

compositions which comprise:

(a) 0.25 to 25 wt.%o, based on the total weight of (a) and (b), of one or more

transfer agents; and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of one or more

barrier materials.

Preferably, the present composition contains:

(a) 1 to 12 wt.%), based on the total weight of (a) and (b), of one or more

transfer agents; and

(b) 88 to 99 wt.%), based on the total weight of (a) and (b), of one or more

barrier materials.

In a second embodiment, the present invention provides novel compositions

which comprise:

barrier materials; and

(b') 0.25 to 35 wt.%), based on the total weight of (a') and (b'), of a mixture,

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b'"), of

one or more skin care agents, provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%, based on the total weight of said composition.

Preferably, in this fifth embodiment, the present composition contains:

(a') 75 to 99 wt.%, based on the total weight of (a') and (b'), of one or more

barrier materials; and

(b') 1 to 25 wt.%), based on the total weight of (a') and (b'), of a mixture, said

mixture comprising:

(b") 1 to 99.9 wt.%, based on the total weight of (b") and (b'"), of one

or more transfer agents; and

(b'") 0.1 to 99 wt.%, based on the total weight of (b") and (b'"), of one

or more skin care active agents,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%o, based on the total weight of said composition.

In a third embodiment, the present invention provides a method for forming a

protective barrier on skin, said method comprising applying an effective amount of a

composition to skin, said composition comprising:

(a) 0.25 to 25 wt.%>, based on the total weight of (a) and (b), of transfer agent;

and

(b) 75 to 99.75 wt.%o, based on the total weight of (a) and (b), of a barrier

material.

Preferably, in this third embodiment, the present composition contains:

(a) 1 to 12 wt.%), based on the total weight of (a) and (b), of one or more

transfer agents; and (b) 88 to 99 wt.%), based on the total weight of (a) and (b), of one or more

barrier materials.

In a fourth embodiment, the present invention provides a method for cleaning

and removing contamination from the skin while forming a protective barrier on skin,

said method comprising applying an effective amount of a composition to skin, said

composition comprising:

(a) 0.25 to 25 wt.%, based on the total weight of (a) and (b), of transfer

agent; and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of a barrier

material.

Preferably, in this fourth embodiment, the present composition contains:

(a) 1 to 12 wt.%), based on the total weight of (a) and (b). of one or more

transfer agents; and

(b) 88 to 99 wt.%, based on the total weight of (a) and (b), one or more

barrier materials.

In a fifth embodiment, the present invention provides a method for applying a

skin care agent to skin, said method comprising applying an effective amount of a

composition to skin, said composition comprising:

barrier materials; and

said mixture comprising: (b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b'"), of

at least one skin care agent,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

Preferably, in this fifth embodiment, the present composition contains:

(a') 75 to 99 wt.%o, based on the total weight of (a') and (b'), of one or more

barrier materials; and

mixture comprising:

(b") 1 to 99.9 wt.%, based on the total weight of (b") and (b'"), of one

or more transfer agents; and

(b'") 0.1 to 99 wt.%, based on the total weight of (b") and (b'"), of one

or more skin care active agents,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

In a sixth embodiment, the present invention provides a method for applying a

skin care agent to the skin, which comprises applying to the skin a composition, said

composition comprising:

(A) 5 to 90 wt.%), based on the total weight of (A) and (B), of one or more

compositions described in the first or second embodiments; and (B) 10 to 95 wt.%), based on the total weight of (A) and (B), of one or more

volatile diluents compatible with the other ingredients of the composition.

In a seventh embodiment, the present invention provides novel compositions

which comprise:

(1) 25 to 80 wt.%), based on the total weight of (1), (2), and (3), of a barrier

material;

(2) 1 to 50 wt.%), based on the total weight of (1), (2), and (3), of lecithin; and

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water.

Preferably, in this seventh embodiment, the present composition contains:

(1) 30 to 60 wt.%, based on the total weight of (1), (2), and (3), of a barrier

material;

(2) 10 to 40 wt.%, based on the total weight of (1), (2), and (3), of lecithin; and

(3) 30 to 40 wt.%), based on the total weight of (1), (2), and (3), of water.

In an eighth embodiment, the present invention provides a method for

applying a skin care agent to skin, said method comprising applying an effective

amount of a composition to skin, said composition comprising:

material;

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water.

Preferably, in this eighth embodiment, the present composition contains:

(1) 30 to 60 wt.%), based on the total weight of (1), (2), and (3), of a barrier

material; (2) 10 to 40 wt.%), based on the total weight of (1), (2), and (3), of lecithin; and

(3) 30 to 40 wt.%), based on the total weight of (1), (2), and (3), of water.

In an ninth embodiment, the present invention provides novel compositions

which comprise:

material; and

(iii) 1 to 50 wt.%, based on the total weight of (i), (ii), and (iii), of chitosan.

Preferably, in this ninth embodiment, the present composition contains:

(i) 5 to 25 wt.%), based on the total weight of (i), (ii), and (iii), of lecithin;

(ii) 15 to 25 wt.%), based on the total weight of (i), (ii), and (iii), of a barrier

material; and

(iii) 10 to 40 wt.%), based on the total weight of (i), (ii), and (iii), of chitosan.

In a tenth embodiment, the present invention provides a method for applying a

composition to skin, said composition comprising:

material; and

(iii) 1 to 50 wt.%), based on the total weight of (i), (ii), and (iii), of chitosan.

Preferably, in this tenth embodiment, the present composition comprises:

(i) 5 to 25 wt.%, based on the total weight of (i), (ii), and (iii), of lecithin; (ii) 15 to 25 wt.%), based on the total weight of (i), (ii), and (iii), of a barrier

material; and

THE TRANSFER AGENT FUNCTION To adhere a hydrophobic barrier material to the skin, especially to wet skin or

skin immersed in water, a bi-functional transfer agent material is employed. This

material has some active groups which are electrostatically positively charged and

some groups which are compatible with the hydrophobic materials of the barrier.

Useful transfer agent materials include various cetyl amine compounds,

various diamines (including for example, Duomeens and Ethoduomeens),

nitroparaffm-derived heterocyclic amines, quaternary ammonium compounds, and the

like. Also useful are compounds of certain cationic polyelectrolytes, including, for

example, polyethyleneimine (PEI) derivatized with varying concentrations of fatty

acids such as, for example, stearic acid, palmitic acid, oleic acid, etc.

Suitable transfer agents are disclosed in U.S. Patent Nos. 5,665,333,

5,888,480, 5,980,868, and 5,961,958 all of which are incorporated herein by reference

in their entirety.

Transfer Agent Materials:

Cationic transfer agent materials useful in the present invention are believed to

attach to the skin via an electrostatic interaction between the cationic portion of the

material and the negatively charged portion of the skin and thus predispose or condition the surface of the skin so that a waxy, hydrophobic material will then adhere

to the surface. Transfer agent materials that are capable of strong electrostatic

bonding to the negatively charged and hydrophilic surfaces of skin include various

straight-chain alkylammonium compounds, cyclic alkylammonium compounds,

petroleum derived cationics, lecithins, and the like.

a) Straight-chain alkylammonium compounds

R R' R

R-N-R" R-N⁺-H X^" R-N⁺-R" X^" I I

R" R'"

R represents a long (C₈.₂₀) alkyl chain which may be substituted with one or more

hydroxy groups, R, R", and R'" each independently may be either a long (C₈.₂₀) alkyl

chain which may be substituted with one or more hydroxy groups or a smaller (C_M)

alkyl groups which may be substituted with one or more hydroxy groups or aryl (C₆.₁₀)

groups or hydrogen, and X^" represents an anion such as chloride or fluoride. These

schematic formulas are given for the purpose of defining the classes of compounds

and represent the simplest concepts of cationic transfer agents whereby one or more

hydrophobic alkyl groups are linked to a cationic nitrogen atom. In many instances

the linkage is more complex as, for example, in RCONHCH₂CH₂CH₂N(CH₃)₂. In

addition, cationic transfer agents may contain more than one cationic nitrogen atom

such as the following class of compounds RNHCH₂CH₂CH₂NH₂ and derivatives

thereof.

Representative examples of compounds according to the above formulas are: cetyl trimethylammonium bromide (CTAB),

hexadecyltrimethylammonium bromide (HDTAB),

stearyl dimethylbenzylammonium chloride,

lauryl dimethylbenzylammonium chloride,

cetyl dimethylethylammonium halide,

cetyl dimethylbenzylammonium halide,

cetyl trimethylammonium halide (bromide, chloride, fluoride),

dodecyl ethyldimethylammonium halide,

lauryl trimethylammonium halide,

coconut alkyltrimethylammonium halide,

N,N-C₈.₂₀-dialkyldimethylammonium halide, and specifically compounds such as

bis(hydrogenated tallow alkyl) dimethylammonium chloride which is known to

adsorb onto the surface with hydrophobic groups oriented away from it, 2-

hydroxydodecyl-2-hydroxyethyl dimethyl ammonium chloride and N-octadecyl-

N ,N',N'-tris-(2 -hydroxyethyl)- 1 ,3-diaminopropane dihydrofluoride.

b) Cyclic Alkylammonium Compounds

A further preferred group of compounds of the present invention which have

been found to be applicable includes a class of surface-active quaternary ammonium

compounds in which the nitrogen atom carrying the cationic charge is part of a

heterocyclic ring. Suitable compounds, for example, are as follows:

laurylpyridinium chloride or bromide,

tetradecylpyridinium bromide, cetylpyridinium halide (chloride, bromide or fluoride).

5-amino-l,3-bis(2-ethylhexyl)-5-methylhexahydro-5-methylpyrimidine (hexetidine)

c) Petroleum Derived Cationics

Typical basic amines are derived from petroleum-based raw materials such as

olefins, paraffins, and aromatic hydrocarbons and include compounds with at least one

aliphatic carbon chain containing six or more carbon atoms attached to the nitrogen.

Thus, amine salts, diamines, amidoamines, alkoxylated amines, and their respective

quaternary salts are applicable.

Preferred compounds of this type include tallow or coco alkyl substituted 1,3-

propylene diamines sold by Witco under the trade names of "Adogen" and "Emcol"

and similar diamines sold by Akzo under the trade name "Duomeen" and their

polyethenoxy derivatives under the trade names of "Ethomeen" and "Ethoduomeens".

d) Polymeric Amines

Suitable polymeric amines comprise a class of polymers containing ionic

groups along the backbone chain and exhibit properties of both electrolytes and

polymers. These materials contain nitrogen, of primary, secondary, tertiary or

quaternary functionality in their backbone and may have weight average molecular

weights as low as about 100 or higher than about 100,000. Representative of these

polymeric cationic transfer agents are the following:

polydimeryl polyamine (General Mills Chemical Co.),

polyamide (trade name "Versamide"), polyacrylamides,

polydiallyldimethylammonium chloride ("Cat-Floe"), polyhexamethylene biguanide

compounds as sold under the trade name "Vantocil", and also other biguanides, for

example those disclosed in U.S. Patent Nos. 2,684,924, 2,990,425, 3,183,230,

3,468,898, 4,022,834, 4,053,636 and 4,198,425,

l,5-dimethyl-l,5-diazaundecamethylene polymethobromide ("Polybrene" from

Aldrich),

polyvinylpyrrolidone and their derivatives,

polypeptides,

poly(allylamine) hydrochloride,

polyoxyethylenated amines, and specifically,

polyethyleneimine ("Polymin" from BASF),

and a class of related and surface active cationic polymers prepared by converting a

fraction of the amino groups to their acyl derivatives. The polyethyleneimine is first

condensed with less than the stoichiometric quantity of acid halides thus alkylating

some of the amino groups and the remaining amino groups are then condensed with

hydrogen halides such as hydrogen chloride or, preferentially, hydrogen fluoride. The

surface activity of these compounds vary with the number of amino groups which are

acylated, and with the chain length of the acylating group RCO-. The condensation

reaction is typically performed with stearic or oleic acid chlorides in the presence of a

solvent containing metal fluoride, preferentially silver fluoride, in such a manner that

silver chloride formed in the reaction precipitates from the solvent, as described in Example XV of U.S. Patent No. 5,665,333, which is incorporated herein by reference

in its entirety.

Also suitable, for the purpose of this invention, are cationic derivatives of

polysaccharides such as dextran, starch or cellulose, for example, diethylaminoethyl

cellulose ("DEAE-cellulose"). Examples of applicable copolymers based on

acrylamide and a cationic monomer are available commercially under the trade name

RETEN from Hercules Inc., or under the name FLOC AID from National Adhesives.

Particular examples of such polymers are FLOC AID 305 and RETEN 220. Similarly

useful are acrylamide-based polyelectrolytes as sold by Allied Colloids under the

trade name PERCOL. Further examples of suitable materials are the cationic guar

derivatives such as those sold under the trade name JAGUAR by Celanese-Hall.

A further preferred group of compounds which comprises a class of water-

insoluble polymers, having nitrogen atoms in their molecules, are quaternary

polymers of quaternary ammonium type, betaine type, pyridylpyridinium type or

vinylpyridinium type. Examples are as follows;

poly(vinyl-benzylmethyllaurylammonium chloride),

poly(vinyl-benzylstearylbetaine),

poly(vinyl-benzyllaurylpyridylpyridinium chloride),

poly(vinyl-benzylcetylammonylhexyl ether) and

quaternized polyoxyethyleneated long chain amines, with the general formula

RN(CH₃)[(C₂H₄O)_xH]₂(-r-) A(-), where A(-) is generally chloride or fluoride, x is a

number from 1 to 20, and R is C₈.₂₂-alkyl. These cationic materials, by reacting with the surface of the skin, produce

strongly hydrophobic films onto which hydrophobic barrier materials are easily

transferred by brushing, rubbing, smearing, or burnishing.

It is important that the reason for this transferability be understood. The

surface of human skin is normally hydrophilic and negatively charged. The transfer

and adhesion of the barrier materials onto such surfaces is difficult or practically

impossible unless the surface is modified by a material that is hydrophobic and

therefore compatible with the barrier materials.

In a preferred embodiment, the transfer agent, a cationic surfactant, is a

polymer which contains a nitrogen atom in a repeating unit and in which a portion of

the nitrogen atoms are quatemized by formation of a salt with a C₈.₂₀ fatty acid,

preferably a C₁₂.₂₀ fatty acid. Examples of such polymeric cationic surfactants include

polyacrylamides, polyvinylpyridines, or polyamines, e.g., poly(ethyleneimine), in

which from 5 to 95 mole%, preferably 40 to 60 mole%, of the nitrogen atoms have

been quatemized by formation of a salt with a fatty acid. Typically such polymers

will have a weight average molecular weight of 600 to 60,000, preferably 600 to

1,800.

In a another embodiment, the transfer agent is a polymer which contains a

nitrogen atom in a repeating unit and in which a first portion of the nitrogen atoms are

quatemized with a C₈.₂₀ fatty acid, preferably a C₁₂.₂₀ fatty acid, and a second portion

of the nitrogen atoms are quatemized by forming a salt with various acids such as

hydrofluoric acid, etc. Examples of such polymeric cationic surfactants include

polyacrylamides, polyvinylpyridines or polyamines, e.g., poly(ethyleneimine), in which from 5 to 95 mole%>, preferably from 40 to 60 mole %, of the nitrogen atoms

are converted to their acid derivatives by reaction with stearic or oleic acid chlorides,

and from 5 to 95 mole%, preferably from 40 to 60 mole%>, of the nitrogen atoms are

quatemized with acetic acid. In this case, the polymeric cationic surfactant will have

a weight average molecular weight of 600 to 60,000, preferably 600 to 1 ,800.

In another preferred embodiment, the transfer agent is a C₈_₂₀-alkylamine

which has been quatemized with citric acid, such as cetylamine citrate.

e) Lecithins

In the present context, the term lecithin includes compounds of the formulae

(I) and (II)

OR² O

+

R^,OCH₂-CH-CH₂-O-P-OCH₂CH₂N(CH₃)₃ (I) O^"

and

OR⁴ O

R³OCH₂-CH-CH₂-O-P-O-CH₂CH₂NH₃ (II) I

O^"

in which R¹, R², R³, and R⁴ are each, independently of each other, a C₁₂_₂₂ saturated or

unsaturated alkanoyl group, such as stearoyl, palmitoyl, oleoyl, palmitoleoyl,

linoleoyl, linolenoyl, arachidonoyl, etc. Also useful in place of lecithins are lecithin-

based compounds such as lyso-lecithins, in which R² is replaced by hydrogen.

Lecithins are described in Kirk-Othmer. Encyclopedia of Chemical Technology. 3rd Ed., Wiley, New York, vol. 14, pp. 250-269 (1981), which is incorporated herein by

reference.

In this embodiment, the lecithin may but does not necessarily function as both

the transfer agent and, according to the known art, as a skin care active agent. The

Examples given below in which lecithin is used alone, in conjunction with waxy

materials, demonstrate a physical protective barrier where lecithin functions as a

transfer agent.

The following is a list of specific commercially available compounds which

can be used as the transfer agent.

I. Primary Amines:

A. Alkyl Amines:

Armeen TD CAS 61790-33-8 AKZO

2. Armeen 18 CAS 124-30-1 AKZO

3. Armeen HT Flake CAS 61788-45-2 AKZO

Adogen 172-D CAS 112-90-3 Witco

Oleoamine

5. Adogen 185 CAS 686-10-26-4 Witco

Etheramine (C12-15)

6. Hexadecylamine CAS 143-27-1 Sigma-Aldrich

II. Secondary Amines:

A. Dialkyl Amines:

1. Armeen 2HT CAS 61789-79-5 AKZO

H₃C(CH₂)₁₇NH(CH₂)₁₇CH₃ 2. Adogen 283 Ditridecylamine Witco

III. Tertiary Amines:

A. Monoalkyl Dimethyl Amines:

1. Adogen 340 (flaked) Trihydrogenated tallow amines Witco

2. Armeen DM 18D CAS 124-28-7 AKZO

B. Dialkyl Monomethyl Amines:

1. Adogen 349 CAS 4088-22-6 Witco

Distearylmethylamine

2. Armeen M2HT CAS 16788-63-4 AKZO

C. Trialkyl Amines:

1. Armeen 316 CAS 28947-77-5 AKZO

Trihexadecylamine

D. Cyclic Amines:

1. Hexetidine 5-amino-l, 3-bis(2-ethyl-hexyl)-5-methylhexa-

hydropyrimidine Angus Chem. Co.

2. Sanguinarine HC1 13-methyl[l,3]benzodi-oxolo[5,6-c]-l,3-

dioxolo[4,5-i]phenanthridium Sigma/ Aldrich

IV. Mixed Primary and Secondary Amines:

A. Fatty Diamines:

1. Adogen 570 S CAS 61791-55-7 Witco

Tallow 1,3-propylenediamine

2. ArosurfAA-57 CAS 68607-29-4 Witco V. Ethoxylated Amines:

1. Ethoduomeen T/l 3 CAS 61790-85-0 AKZO

2. Ethoduomeen T/20 CAS 61790-85-0 AKZO

3. Ethoduomeen T/25 CAS 61790-85-0 AKZO

4. Ethomeen 18/12 CAS 10213-78-2 AKZO

VI. Amine Salts:

Duomeen TDO CAS 61791-53-5 AKZO

2. Cetvlamine Hvdrofluoride H,C⁽CH.VNH,⁺F- (GABA #2

3. Armac HT CAS 61790-59-8 AKZO

VII. Polyamines:

A. Di- and Triamines:

1. Duomeen S CAS 61791-67-1 AKZO

2. Duomeen T CAS 61791-55-7 AKZO

H₂N(CH₂)₁₈NH₂

VIII. Quaternary Ammonium Salts:

A. Alkyltrimethyl Ammonium Salts:

1. Cetyltrimethyl ammonium bromide CAS 57-09-0

Sigma-Aldrich

2. Arquad T-50 Tallow alkyltrimethyl ammonium bromide

AKZO

B. Dialkyldimethyl Ammonium Salts:

1. Arquad 2HT-75 Bis(hydrogenated Tallow-alkyl)dimethyl

ammonium chloride AKZO 2. Bardac 2280 Didecyldimethyl ammonium chloride

Lonza

C. Trialkylmethyl Ammonium Salts:

1. Adogen 316 Tricetylmethyl ammonium halide Witco

2. Adogen 422 Behenyltrimethyl Ammonium chloride

Witco

D. Benzylalkyl:

1. Arquad DMHTB-75 Dimethylbenzyl hydrogenat ed tallow

ammonium chloride AKZO

2. Barquat MB-80 Alky ldimethylbenzyl ammonium

chloride Lonza

IX. Imidazolinium Quats:

1. Varisoft 475 CAS 68122-86-1 Witco

X. Pyridinium Quads:

A. Pyridinium Halides:

1. Cetyl Pyridinium Chloride CAS 6004-24-6

XI. Poly electrolytes:

A. Polymeric Quats:

1. Cat-Floe PL CAS 26062-79-3 Calgon

Polydimethylallylammonium chloride

2. Cat-Floe L CAS 26062-79-3 Calgon

Polydimethylallylammonium chloride 3. Cat-Floe T-2 CAS 26062-79-3 Calgon

Polydimethylallyl ammonium chloride

XII. Amphoteric Compounds:

A. Betain Derivatives:

1. Amphosol CG Coco amido betain Stepan

2. Amphosol CA Coco amido betain Stepan

B. Proteins and related compounds with isoelectric points greater than

physiologic pH (i.e., those which are positively charged when

dissolved in body fluids).

1. Type A Gelatin 200 Proteins Kind-Knox

2. N.N-Di-Methylated Casein Methylated protein

Sigma-Aldrich

Armeen Z CAS 68469-05-08 AKZO

N-coco β amidobutyric acid

C. Lecthins

1. Lecithin (from egg yolk) Phosphatidylcholine

Sigma-Aldrich

2. Lecithin (from soy bean) Phosphatidylcholine

Sigma-Aldrich

3. Lecithin (Ultralec) Phosphatidylcholine

Archer Daniels Midland

4. Lecithin (YelkinoD Phosphatidylcholine

Archer Daniels Midland 5. Natural Egg Yolk Phosphatidylcholine

Source of lecithins: Grocery store

THE BARRIER MATERIAL FUNCTION

Now having a mechanism for adhering a protective, hydrophobic material to

the skin, any of several hydrophobic barrier materials may be selected to perform this

function. A microcrystalline wax or a high molecular weight polydimethylsiloxane,

for example, are barrier materials which provide an adherent, conformal, hydrophobic,

continuous, inert, colorless or near-colorless barrier. This hydrophobic waxy or

polymeric barrier appears to endure in place and function indefinitely or until it is

intentionally removed or sloughed off in the normal process of cellular turnover.

Thus, with the transfer and barrier functions performed, extended protection is

provided against deleterious activities since the treated skin is coated and protected.

In use, the compositions of the present inventions are sprayed, brushed, or

rubbed on the skin, even wet skin or skin immersed in water. Importantly, barrier

materials are amorphous materials which shear or cleave easily so that materials

which may adhere to the surface of the barrier may be removed easily by the

application of moderate shear forces. This same low-shear characteristic moves the

barrier materials about, exposing any active agent substances blended into the barrier

materials.

Suitable barrier materials are disclosed in U.S. Patent No. 5,665,333 and U.S.

Patent 5,980,868, which are incorporated herein by reference in their entirety. Hydrophobic Barrier Materials

It has been found that various hydrophobic compounds of high molecular

weight, solid at body temperature and generally similar to fats and waxes are useful as

barrier forming materials. Typically they are long chain hydrocarbons, especially

normal paraffins having a chain length of 16 carbons or greater, paraffins with several

loci of branching and unsaturation, where the extent of such branching and

unsaturation does not lower the solidification point below body temperature, and

show essentially no solubility in water or other aqueous materials. The major types of

these wax-like materials belong to two basic categories:

I. Natural waxes of animal, vegetable or mineral origin such as beeswax,

lanolin, spermaceti, carnauba wax, petroleum waxes including paraffin waxes,

microcrystalline petrolatum and microcrystalline wax; and

II. Synthetic materials including ethylenic polymers such as polyethylene

glycols ("Carbowax"), polymethylene wax ("Paraflint") and various hydrocarbon

types as obtained via Fisher-Tropsch synthesis.

Other suitable materials include silicone-based polymers such as

polymethylalkylsiloxanes, polydimethylsiloxanes, poly(perfluoroalkylmethyl

siloxanes), poly(methyl-3,3,3-trifluoropropyl siloxanes) and various aromatic (phenyl

containing) siloxanes as sold by United Chemical. Also useful are various fiuoropolymers where some or all of the hydrogen is

replaced by fluorine, including, among others: polytetrafluoroethylene (PTFE);

fluorinated polyethylene-propylene (FEP);

perfluoroalkoxy (PFA) polypropylene-polyethylene;

polyvinylidene fluoride (PVDF); and

polyvinylfluoride (PVF).

THE SKIN CARE ACTIVE AGENT FUNCTION

Experimentation with the technology of the present invention demonstrates

that many materials known in the art of skin care to provide medical or cosmetic

benefits to the skin may be incorporated into the composition of the present invention

to enhance the known benefits of such skin care active agents. Through incorporation

of known skin care active agents into compositions of the present invention, the

known effects of such materials may be improved, by providing greater

concentrations of the active agents to come into contact with the skin, by providing

longer or extended contact of the active agent with the skin, by preventing removal of

the active skin care agents by sweating, washing, swimming, or incidental contact, or

by providing for more effective and efficient application of active skin care agents to

wet skin, even to skin immersed under water.

In addition, some of the skin care agents tested and described in the Examples

below migrated out or diffused away from the areas on which a Protective Coating

(PC) was applied so that, to some extent, the skin care function extended to areas not

reached by the PC itself. These skin care agents may be blended into the barrier material so that, as the barrier material is sheared, cleaved, disturbed, eroded, abraded,

etc., fresh skin care agent is exposed and freed to function. Alternatively, certain

undesirable or "side" effects of some skin care active agents, such as, for example,

irritation, may be mitigated by incorporating the skin care active agent into the present

invention, thus providing improved tolerance of the patient to the active agent.

Such skin care active agents include, but are not limited to,

Acetic Acid

Aclometasone Dipropionate

Acyclovir

Alclometasone Dipropionate

Aluminum Chlorhydrate

Aluminum Chlorhydroxide

Aluminum Chloride Hexahydrate

Amcinonide

Aminobenzoate Potassium

Ammonium Lactate

Ammonium Mercury

Amphotericin B

Anthralin

Antimicrobial Agents

Bacitracin

Balsam Peru

Benzocaine Benzoin Compoundecylenate

Benzoyl Peroxide (BPO)

Beta-Carotene

Betamethasone Acetate

Betamethasone Dipropionate

Betamethasone Sodium Phosphate

Betamethasone Valerate

Butaconazole Nitrate

Butamben Picrate

Canthardin

Carbol Fuchsin

Castor Oil

Cetylpyridinium Chloride

Chloramphenicol

Chlorcyclizine

Chlorhexidine

Chlorhexidine Acetate

Chlorhexidine Gluconate

Chloroxine

Chloroxynol

Ciclopirox Olamine

Clindamycin HC1

Clioquinol Clobetasol Propionate

Clocortolone Pivalate

Clotrimazole

Coal Tar

Collagenase

Cortisone

Cortisone Acetate

Crotamiton

Cyclopentolate HC1

Dapsone

Desonide Desoxymetasone

Desoxyribonuclease

Dexamethasone

Dexamethasone Acetate

Dexamethasone Sodium Phosphate

Dibucaine

Dichloroacetic Acid

Dichlorophene

Diflorasone Diacetate

Diperodon

Econazole Nitrate

Ephedrine HC1 Erythromycin

Estradiol

Etretinate

Fibrinolysin

Flucinolone

Flucinolone Acetonide

Fluocinonide

Fluorouracil

Fluradrenolone

Flurandrenolide

Fluticasone Propionate

Formaldehyde

Gentamycin Sulfate

Gramicid

Griseofulvin

Guaifenesin

Halcinonide

Halobetasol Propionate

Haloprogin

Hexachlorophene

Hexetadine

Hyaluronidase

Hydrocodone Hydrocortisone

Hydrocortisone Acetate

Hydrocortisone Butyrate

Hydrocortisone Sodium Phosphate

Hydrocortisone Sodium Succinate

Hydrocortisone Valerate

Hydroquinone

Hydroxyzine HC1

Hydroxyzine Pamoate

Iodine

Iodochlorhydrocodone

Iodoquinol

Isotretinoin

Ketoconazole

Lactic Acid

Lecithin

Lidocaine Hydrochloride

Lindane

Mafenide Acetate

Meclocycline Sulfosalicylate

Methoxsalen

Methylprednisone

Methylprednisone Acetate Methylprednisone Sodium Succinate

Metronidazole

Miconazole Nitrate

Minoxidil

Mometasone Furoate

Monobenzone

Mupriocin

Naftifine HC1

Neomycin Sulfate

Nitrofurazone

Nystatin

Octyl Methoxycinnamate

Oxybenzone

Oxyquinoline Sulfate

Papain

para-Aminobenzoic Acid

Permethrin

Phentermine HC1

Podophylum

Polymyxin B Sulfate

Potassium Iodide

Pramoxine HC1

Prednicarbate Prednisolone Sodium Phosphate

Prednisone

Pseudoephedrine

Pyro gallic Acid

Retinoic Acid

Retinol

Salicylic Acid

S aluminum Acid

Scarlet Red

Selenium Sulfide

Silver Nitrate

Silver Sulfadiazine

Sodium Sulfacetimide

Sodium Thiosulfate

Streptokinase

Sulconazole

Sulconazole Nitrate

Sulfabenzamide

Sulfacetamide

Sulfanilamide

Sulfathiazole

Sulfur

Sunscreen Agents Sutilains

Terconazole

Tetracaine

Tetracycline

Tretinoin

Triacetin

Triamcinolone

Triamcinolone Acetonide

Triamcinolone Diacetate

Trimeprazine Tartrate

Trioxsalen

Triple Dye

Trypsin

Undecylenic Acid

Urea

Vitamins (all)

Zinc Oxide

Zinc Undecylenate

and other agents known in the art to have medical, cosmetic, bactericidal, or other

effects on the skin.

In addition, the present composition may also include coloring materials or

fragrances to mask any color or odor of the other ingredients or to provide a more

desirable appearance and smell. The fragrance or color may be present in an amount conventionally used for imparting the desired color or scent, typically 0.01 to 5 wt.%,

preferably 0.1 to 1.0 wt.%, based on the total weight of the composition.

The present compositions may also include manufacturing aids, modifiers and

thickeners, diluents, solvents, emulsifiers, stabilizers, and ingredients which enhance

the aroma, appearance, opacity, color, texture, or any other attribute of the

composition.

Thus, the present skin care compositions contain, at minimum, a barrier

material, such as wax or other hydrophobic polymer, and at least 0.25 wt.%> of a

transfer agent, which is a compound having one region which is relatively

hydrophobic, such as a hydrocarbon chain, and one portion which is positively

charged under use conditions, such as a quaternary nitrogen. Anionic materials such

as anionic surfactants can quantitatively neutralize a transfer agent by reacting with

the positively charged group. Accordingly, addition of any quantity of an anionic

surfactant to the present skin care composition will decrease the activity of the transfer

agent, and, if enough anionic agent is present, the transfer agent will no longer

function.

Thus, the present skin care compositions preferably contain at least 0.25 wt.%

of transfer agent above and beyond the amount of transfer agent which is neutralized

by any neutralizing anionic reagent also present in the composition (or, in alternative

language, the present skin care compositions contain at least 0.25 wt.%> of a transfer

agent not including the amount of transfer agent which is neutralized by any

neutralizing anionic reagent also present in the composition). More preferably, the

present skin care compositions preferably contain at least 1 wt.% of transfer agent above and beyond the amount of transfer agent which is neutralized by any

neutralizing anionic reagent also present in the composition. Most preferably, anionic

reagents of any kind should not be included in the present skin care composition

unless provision is made to physically separate, for example, by encapsulation, the

anionic reagent from the cationic transfer agent.

It should be realized that many anionic reagents contain more than one anionic

functional group. In such cases, one mole of the anionic reagent may neutralize more

than one mole of the transfer agent, and the amount of transfer agent which will be

neutralized by the anionic reagent is calculated by taking into account the number of

equivalents of anionic neutralizing groups contained in the anionic reagent.

Similarly, soluble compounds with anionic groups which may, for example,

remain on the skin after washing with an anionic detergent, can decrease the

effectiveness of the present skin care compositions by neutralizing or partially

neutralizing the transfer agent. Ordinarily, however, the amount of soluble anionic

reagents remaining on skin after washing and thoroughly rinsing will be so small

(100- to 100,000-fold lower than the transfer agent) as to inactivate only a very small

percentage of the transfer agent, thus having no material effect of the performance of

the present skin care compositions.

In the context of the present invention, such anionic reagents include those

compounds which contain anionic functional groups which can be thought of as being

obtained by the neutralization of a strong acid, i.e., the neutralization of a sulfonic

acid to obtain a sulfonate. Such anionic reagents, of course, include anionic

surfactants. Anionic surfactants are disclosed in McCutcheon's: Volume 1 : Emulsifiers and Detergents, North American and International Editions, Pub. by

McCutcheon's Division, The Manufacturing Confectioner Publishing Co., Glen Rock,

NJ USA, which is incorporated herein by reference.

Particularly important classes of anionic surfactants include: sulfates,

sulfonates, oxysulfates, and ether sulfates of fatty acids, fatty acid esters, alcohols, and

petroleum derivatives, their salts, their aryl, alkyl, and arylalkyl derivatives, and

similar synthetic compounds, including but not limited to members of the following

groups:

Compound Manufacturer^*

Avirol series Henkel

Abex series Rhone-Poulenc

Barium Petronate series Witco

Alpha-step Stepan

Alox series Alox

Actrasol series Climax Performance Chemicals

Aristonate series Pilot Chemical

Astromid series Alco

Astrowet series Alco

Arylenes Huntsman

Avenel S series PPG

* Manufacturers addressed are listed in McCutcheon's, reference cited above.

Sulfoccinates, including but not limited to members of the following groups:

Aerosol series Cytec Industries Carboxylated aryl, alkyl, and arylalkyl alcohols and their derivatives, including but

not limited to members of the following groups:

Abex 3594 Rhone Poulenc

Aryl, alkyl, and arylalkyl phosphate esters, their sodium salts, and derivatives,

including but not limited to members of the following groups:

Acrilev OJP Finetex

Alkylene series Hart Products

Actrafos Climax

Amphisol series Givaudan-Roure

Barisol series Dexter

Fatty acid derivatives of organic acids, including but not limited to members of the

following groups:

Amisoft series Ajinomoto USA

Protein based compounds and their derivatives, including but not limited to members

of the following groups :

Aminofoam C Croda

Atrasein 115 Atramax

Organosilane and organosiloxane sulfates, sulfonates, thiosulfates, and their

derivatives, including but not limited to members of the following groups:

Abil S-201 Goldschmidt

The present compositions may be prepared by a method in which the barrier

material is first suspended or dissolved in an appropriate solvent (e.g. xylene, toluene, petroleum ether, methanol, ethanol, methyl ethyl ketone, or where, for example,

aqueous dispersions of fluorocarbons are selected as barrier materials, water). The

transfer agent(s) and, optionally, skin care agent(s) are then added and the solvent

removed by, e.g., evaporation. The present compositions may also be prepared by

direct mixing of the barrier material and the other ingredients, either stepwise or all

together, at or above the melting point of the barrier material, if the other ingredients

are stable or will tolerate for a sufficient time such a temperature.

As noted above, one embodiment of the present invention provides

compositions which comprise lecithin. Lecithin is a naturally occurring group of

phospholipids that is found in nearly every living cell. The food industry has long

recognized lecithin as a lipophilic emulsifier used in products like margarine and

chocolate. Lecithin lends itself to specific modification techniques to extend the

functionality and physical characteristics of lecithin far beyond their natural variations

to include a wider range of functionalities such as dispersion, lubrication, and wetting

which also involve enhanced specificity of bonding to oppositely charged surfaces.

For example, removing oily components, such as triglycerides and fatty acids, from

lecithin a significant enhancement in positively charged components is realized.

Also as noted above, one embodiment of the present invention provides

compositions which comprise chitosan. Such compositions provide an effective and

practical approach to control skin problems in animals. A combined action of natural

products such as chitosan and lecithin permits an effective delivery of a waxy barrier

to the animal's skin on a continuous basis. Chitosan is a natural product derived from

chitin, a polysaccharide found in the exoskeleton of shellfish like shrimp or crabs. It possesses many of the same properties as plant fibers, however, unlike plant fibers, it

has the ability to bind fat significantly, acting as a "fat storage." Chitosan has been

reported to have antibacterial properties and also to inhibit formation of plaque/tooth

decay. Chitosan is derived from chitin by removing and refining the acetyl groups

through a process called de-acetylation. This process converts the neutral chitin

molecules into molecules with a strong positive polarity. This positive polarity

attracts the chitosan molecule to negatively charged surfaces by ionic interactions

(similarly as a magnet attracts steel). Chitosan is commercially available from, e.g.,

Aldrich Chemical co. 1001 west St. Paul Ave., Milwaukee, WI 53233. A strong

affinity of chitosan for fatty or waxy substances makes it an ideal matrix material to

bind and confine the present compositions into a self-cohesive and granular form

easily incorporated into skin care formulations. The granular form of the final product

is not tacky and is easy to handle.

The present method of application may be carried out by contacting the

present composition with the skin to effect transfer of the composition to the skin. In

a preferred embodiment, the present compositions are applied to human or animal

dermis, epidermis, and/or stratum comeum. The exact means of contacting will

depend of course on the nature of the composition and/or applicator. Thus, in the case

of an atomizer, spraying will suffice to apply the compositions, while creams may be

applied with a swab, brush, puff, or by hand.

Thus, the compositions may be applied to the skin to form a "breathable"

barrier which can effectively be applied to wet or dry skin to: 1. Produce cosmetically and medically desirable effects through the barrier

function alone, without inclusion of a medicament, cosmetic, or other active

ingredient; and

2. Carry known or yet to be discovered medicaments, cosmetic, or other

active agents and hold them in contact with the skin in higher concentrations, and/or

for extended periods of time, and/or in a more aesthetically desirable condition to

provide performance superior to the same ingredients when applied to the skin via

conventional vehicles.

Accordingly, the present compositions and methods may be used to prevent,

treat, cure and relieve symptoms of diseases and conditions of the skin, internal and

external membranes, mucosa, blood, lymphatic and other vessels and glomeruli of the

body and its organs including systemic disease and conditions having primary or

ancillary signs or symptoms manifesting in or on the skin, internal and external

membranes, mucosa, blood, lymphatic and other vessels and glomeruli of the body

and its organs, including but not limited to allergies, dermatitises, dermatoses,

bacterial, fungal, and parasitic infestations and infections, abrasions, lacerations, cuts,

bums, and other insults and injuries resulting from or related to injury or normal or

abnormal metabolic, pathologic, or immunological processes. Such diseases and

conditions include but are not limited to acne, athlete's foot, jock itch, ringworm,

hemorrhoids, nail infections, skin infections, sunburn and sun- or injury-induced

pigmentation, psoriasis, seborrhea, eczema and other dermatitises, dermatoses, and

other diseases and pathological processes including kidney diseases, atherscleroses, etc. listed in Dorland's Illustrated Medical Dictionary, Stedman's Medical Dictionary,

and other sources.

The present compositions and methods are useful to minimize the appearance

of skin imperfections, to help shed dry, damaged cells and unclog pores, to

moisturize, exfoliate, and reveal younger-looking skin, to ameliorate and minimize the

visible signs of aging, to ameliorate, minimize, and manage complexion problems, to

gently peel away outer layers of dry, sun-damaged skin to expose younger looking

skin, to leave skin smooth, soft, and refreshed, to ameliorate or minimize cosmetic

problems associated with dry, sensitive, normal, combination-oily skin, to help

control oily or problem-prone skin, to soothe the skin, improve skin texture, and

restore moisture to the skin, to smooth fine lines in the skin, to even skin tones, to

refine the texture of the skin, to improve and treat acne-prone skin, to protect against

environmental skin aging, to lighten pigmented areas, and to enhance and accelerate

the results achieved with other products.

Thus, the present composition may take the form of:

1. Makeup

2. Makeup Foundation

3. Makeup Remover

4. Eye Makeup

5. Eye Makeup Remover

6. Eye Makeup Pencil

7. Eye shadow

8. Facial Cream 9. Facial Cleanser

10. Facial Emulsion

11. Facial Mask

12. Facial Makeup

13. Facial Scrub

14. Hand Cream

15. Body Cream

16. Sun Tan Lotion (including Sun Screen)

17. Lotion

18. Baby Oil

19. Baby Lotion

20. Anti -Aging Cream

21. Night Cream

22. Vanishing Cream

23. Cold Cream

24. Balm

25. Skin Conditioner

26. Disposable Wipe

27. Baby Wipe

28. Cleansing Cream

29. Lip Conditioner

30. Chap Preventative

31. Wound Care Ointment 32. Foundation for Lipstick (when applied to the lips before applying lipstick, the

present composition locks or bonds the lipstick in place; no "feathering" or

"bleeding" takes place and it looks as good 10 hours after application as it did

just following application.)

33. Ingredient in Make-Up (lasts longer and goes on wet)

34. Anti-Perspirant/Deodorant

35. Wound Care (anti-adhesion, anti-infection, may contain antibiotic, e.g.,

Neosporin, etc.)

36. Surgical Site Wound Care

37. Implants (can provide anti-adhesion, anti-infection benefits when applied to

the skin or tissues in contact with implants, e.g., pacemakers, etc. or on certain

surfaces of the implant itself. Many conventional pacemaker implants produce

infections which require removal and re-implantation. Application of the

present composition to the skin or tissues in contact with the implant or on

certain surfaces of the implant itself may prevent the adhesion of surrounding

tissues to the implant, where desirable and also prevent or decrease the rate of

infection, especially when the present composition comprises one or more

anti-bacterial agents.)

38. Indwelling Instruments (the present composition may provide anti-adhesion

and anti-infection benefits when applied to the skin or tissues in contact with

indwelling instruments, e.g., catheters, etc. or on certain surfaces of the

indwelling instrument itself.) 39. Surgical Sites, Instruments, Sutures (coating surgical instruments and/or

sutures with the present invention may provide anti-adhesion and anti-

infection benefits and may reduce the resistance to placing the sutures by

reducing the frictional resistance of the sutures.)

40. Athlete's Foot (the present invention even without an active agent may

provide benefits; hexetidine is not only a preferred transfer agent but also a

good anti-fungal material as well as a weak anti-bacterial material; thus,

compositions which contain about 5% by weight hexetidine provide extended

contact time with the affected area.)

41. Jock-Itch (jock-itch is caused by the same fungus responsible for athlete's foot

and application of the present composition to the affected area may be

effective for the prevention and/or treatment of jock-itch.)

42. Anti-Itch (the present compositions may be used as anti-itch compositions,

even without inclusion of an active agent, especially when the itching is

caused by external stimuli; traditional ani-itch agents, e.g., hydrocortizone

may also be included in the present compositions.)

43. Diaper Rash (the present compositions may be applied to the affected area or

to the diaper itself to combat diaper rash.)

44. Anti-Wrinkle Products (the present composition may be used to reduce

wrinkles even without the presence of an active agent; alternatively, the

present composition may contain an anti-wrinkle active agent such as shark

liver oil.) 45. Anti- Anal Itch (the present composition may be applied to the affected area to

combat anal itch even without an added active agent; traditional ani-itch

agents, e.g., hydrocortizone may also be included in the present compositions;

the ability of the present compositions to adhere to moist surfaces means that it

will stay in place longer and require fewer applications.)

46. Muscle Rub (compositions according to the present invention which contain a

circulation-stimulating active agent, e.g., capsicum, etc. may be applied to the

skin to treat sore or stiff muscles; the adherence of the present compositions to

the skin means that the circulation-stimulating active agent (and resultant heat)

will remain in contact with the affected area longer.)

47. Poison Oak, Ivy, Sumac, Etc. (the present compositions may be applied to the

skin prior to engaging in activity which would bring the skin into contact with

poisonous plants, e.g., poison ivy, poison oak, poison sumac, etc. and serve as

a prophylactic barrier even without an active agent; the present compositions

may also be applied to skin already suffering from poison ivy, poison oak,

poison sumac, etc. to reduce the itching and spread of the condition with or

without an anti-itching active agent.)

48. Depilatory Enhancer (hair absorbs moisture and is then more easily cut and/or

removed; application of the present composition allows the depilatory to be

applied when the hair is wet, thereby enhancing the cutting and/or removal of

the hair.)

49. Anti-Drying (the present compositions may be used to form a protective

barrier on the skin to prevent loss of moisture and/or oils from the skin.) 50. Other forms which will be apparent to those skilled in the art.

It should be understood that in the above-listed applications, the present

composition may comprise either: (1) a transfer agent and a barrier material; or (2) a

transfer agent, barrier material, and active agent. In other words, for the applications

listed above, good effects may be achieved even without the addition of an active

agent, but in certain situations it may be advantageous and/or desirable to add an

active agent.

The present compositions are typically applied to the skin in an amount

effective to provide a protective barrier on the skin, usually about 80 micrograms to

about 0.5 grams per cm² of skin, preferably 100 micrograms to 0.1 grams per cm² of

skin.

Although the present invention has been described in detail in the context of

skin care compositions and methods for treating the skin, the present compositions

may be applied to substrates other than skin and may be used in methods other than

skin care. In particular, it should be understood that the present compositions may be

used in the following non-skin care applications.

1. Mold releases and casting adhesives. The release of a cast article from a mold

may be enhanced by application of the present composition to the interior

surface of the mold, or to the object to be cast or molded. This method may be

especially effective for enhancing the release of a cast article made from a

hydrophilic material (certain plastics and ceramics) from a mold which has a

hydrophilic interior surface. . Ink and dye processing. The present compositions may be used to enhance the

adherence of a hydrophobic ink to a hydrophilic substrate or vice-versa. In

particular, the hydrophilic substrate may be coated with the present

composition either over the entire surface or in a pattemwise fashion.

Application of the present composition to a hydrophilic surface may also be

used to advantage in batik and tie-dye processes.

3. Anti-fouling applications. In marine applications, the present compositions

may be applied to surfaces subject to fouling without hauling-out due to the

ability of the present compositions to be applied to wet surfaces. The present

compositions are useful as anti-fouling agents with or without active agents

such as antibacterial agents. This is an important advantage, since most of the

traditional anti-fouling materials, e.g., tin, copper, etc., are toxic to some

marine organisms. When coated on a ship's hull, the present compositions

may inhibit the attachment of marine growth to the hull or reduce the

adherence of marine growth to the hull such that moving through the water at a

speed of a few knots may be sufficient to remove any marine growth. In

addition, the turbine blades of hydroelectric generators are plagued with

fouling. Application of the present composition may be effective for reducing

the fouling of turbine blades even in the face of the large shear forces

encountered by turbine blades.

4. Leather treatments. Oils are destructive to leathers; they soften them and

allow them to stretch and/or crack and they provide an attachment for grit and

abrasives. Waxes are the preferred protectants. However, waxes applied directly to leathers are easily removed. Application of the present composition

to leather provides extended benefits and reduced drying. In addition, since

the outer layers slough off, less dirt will adhere to the leather.

5. Auto, vehicle protection. Application of the present composition to the

interior and exterior surfaces of automobiles and other vehicles may be

effective for protecting and/or enhancing the appearance and endurance or

longevity of those surfaces. This may be especially effective for protecting

hydrophilic surfaces such as certain seat coverings or other materials.

6. Wood protectant. Wood is negatively charged on the surface and contains

moisture. The present compositions may thus be used as a furniture polish

with excellent results, especially when rubbed down to a very thin but

protective hydrophobic layer. The present compositions prevent water

damage, e.g., water rings and stains. The present compositions may also be

used to prevent wood from swelling, as in wood casement windows, and

protect against mildew.

7. Metal treatments. The present compositions may be applied to metals to

protect against oxidation, staining, chemical attack, and tarnishing.

8. Ceramic sealant. The present composition may be applied to certain ceramics

to prevent and/or reduce the staining or fouling of the ceramic. For example,

the present composition may be applied to showers, bathtubs, ceramic tile, and

grout to prevent the formation of mold and mildew stains and bathtub rings.

9. Painted surfaces. The present composition may be applied to painted surfaces

to afford a protective surface. 10. Floor wax. The present composition may be used as a floor wax, especially on

floors with a hydrophilic surface, such as wood floors.

11. Anti-graffiti coatings. The present composition may be applied to surfaces

which are subject to graffiti attacks, such as buildings, billboards, train cars,

etc. The hydrophobic barrier afforded by the present composition not only

makes it more difficult to apply the graffiti in the first place but also makes it

easier to remove graffiti which is applied.

12. Paper and cardboard coatings. The present composition may be applied to

paper or cardboard to obtain a moisture resistant barrier. This application may

be useful not only for protecting the contents of a paper or cardboard package

from water or moisture damage, but also for preparing a paper or cardboard

package suitable for storing liquids such as milk or juice.

13. Plastics and fiberglass. The present composition may be applied to plastics or

fiberglass to protect, lubricate, seal, or waterproof the plastic or fiberglass.

14. Anti-stick coatings. The present coatings may be applied to the cooking

surfaces of cooking utensils, pots, pans, etc. as an anti-sticking agent. In such

applications, it may be desirable to formulate the present composition with a

volatile propellant and to apply the composition by means of an aerosol can.

15. Glass or china protectant. The present composition may be applied to glass or

china to form a protective barrier which will keep the surface cleaner.

16. Pesticides. The present composition may be formulated with an active agent

which is a pesticide and applied to any surface which is susceptible to

infestation by pests. In a preferred embodiment, the present composition which contains the pesticide may be applied directly to the leaves or foliage of

a plant.

17. Anti-fogging, anti-condensation agent. The present composition may be

applied to surfaces which are susceptible to fogging, e.g., bathroom mirrors,

windshields, eyeglasses, etc.

18. Adhering lubricants to substrates. Application of the present composition to

the surface of a substrate is useful for adhering a lubricant such as a wax,

grease, petrolatum, teflon, or silicone to the surface of the substrate. In certain

situations, it may be preferred or necessary to pretreat the surface of the

substrate so that the present composition will itself adhere to the substrate.

The present compositions and methods provide a number of advantages which

are not achieved by conventional compositions. In particular, the present

compositions are characterized by the following advantages:

1. The present compositions are easily applied to a wet substrate. This advantage

is particularly important in the context of skin care as in many circumstances it

is desired to apply a skin composition to wet skin.

2. The present compositions bond well to the skin or other substrate resulting in a

greater adhesion of the hydrophobic barrier.

3. The present compositions are resistant to removal. Mechanical action is often

required to remove them from the skin or other substrate, since the barrier is

not easily removed by solubility in aqueous, alcohol or other common

personal care systems, but only by organic solvents such as hexane, etc., which

are rarely encountered in skin care treatments or compositions. 4. The present compositions extend the time of contact with the skin or other

substrate. This is an especially important benefit. Enhanced contact time

means enhanced protection afforded by the protective hydrophobic barrier and

longer contact time with any active agent present.

5. Enhanced activity of the active agent. The extended contact time exhibited by

the present compositions may result in intensifying the benefits of any active

agent present in the composition according to the present invention.

6. The present compositions provide a moisture barrier in both directions. In

other words, the present compositions are able to keep moisture from escaping

from the skin and are thus useful as moisturizers. In addition, the present

compositions are also effective for keeping excessive moisture away from the

skin and are thus useful for treating conditions related to contact of excess

moisture with the skin, e.g., athlete's foot.

7. The present compositions are effective even without the addition of an active

agent. In many cases, e.g., anti-perspirants, the combination of the transfer

agent and the barrier material alone may provide the desired benefits even

without the addition of an active agent. This is an important advantage. The

barrier materials in many cases do not inhibit epidermal transpiration. Thus,

the present compositions form a "breathable" protective coating. This coating

may deny access to the skin or other substrate by bacteria, moisture, acids, and

other toxic or contaminating substances. Permeability /Porosity/Discontinuity:

The 'porosity', in the general or non-technical use of that word, or, more

specifically, the permeability or continuity of the barriers formed by the compositions

of the present invention, may be controlled by selection of viscosity modifiers, their

molecular weights and their concentrations in the formulations of the compositions of

the present invention. In general, higher molecular weight materials increase cohesion

between the molecules of the barrier materials and reduce the permeability or

'porosity' of the resulting composition when applied.

In addition, transfer agents vary in the extent to which they diffuse through the

barrier material selected, so that some transfer agents, such as hexetidine, having a

high mobility or diffusability in microcrystalline wax barriers, will demonstrate a high

degree of permeability in the barriers formed by the compositions of the present

invention and may carry with it other ingredients, such as certain of the active agents,

providing permeability of the active agent both to the substrate and to the surfaces

presented to the outer environment.

Characteristics of the substrate may also affect the observed permeability of

the barriers formed by the compositions of the present invention in application.

Selecting very low molecular weight barrier materials may result in a very thin

coating of as little as a single molecular layer of transfer agent combined with a single

molecular layer of the barrier material with the functional continuity or porosity of the

composition then more importantly dependent upon the characteristics of the substrate

to which it is applied. Specifically, it is possible to vary the permeability of the barrier to various

substrates by varying the composition and/or concentrations of the barrier material,

the transfer agent, viscosity modifiers, and active agents either independently or

proportionately with respect to each other. In addition, the permeability of the barrier

formed by the composition of the present invention will necessarily vary with respect

to the specific permeant and with the environment in which it exists, e.g., the

solubility of the transfer agent in the environment of the surfaces of the barrier formed

by the composition of the present invention not in contact with the substrate.

Surface Energy (including Surface Tension/Critical Surface Tension/Interfacial

Tension):

In many applications, the surface energy (SE) of the barrier formed by the

composition of the present invention will have important implications in functionality.

For example, during experimentation and testing of barriers formed by the

compositions of the present invention on dental surfaces, it was found that S. mutans,

an important organism in oral care pathogenicity, will not attach to surfaces having an

SE below a certain level. However when the SE is too low, the product can become

aesthetically undesirable since the tongue cannot wet the surface of the barriers

formed by the compositions of the present invention and the patient or user of the

product is repeatedly frustrated in trying to do so. Thus a specific range of SEs is

important in this application. There are several factors which, independently and in combinations among

them, may alter or affect the SE of the resulting barriers formed by the compositions

of the present invention. Among them are:

1. Selection of the transfer agent(s)

2. Concentration of the transfer agent(s)

3. Solubility of the transfer agent(s) in the environment at the interface of the

barrier formed by the composition of the present invention.

4. Selection of the barrier material(s)

5. The rate of permeability/mobility /diffusability of the transfer agent(s)

through the barrier formed by the composition of the present invention (for example

as a function of the rate and extent to which the transfer agent(s) are replenished at the

environmental interface as outer layers of the barrier formed by the composition of the

present invention are removed); and that rate with respect to the rate of mobility of

active agents through the materix of the barrier formed by the composition of the

present invention, etc.

6. Characteristics of the environment, such as pH, etc.

Other features of the invention will become apparent in the course of the

following descriptions of exemplary embodiments which are given for illustration of

the invention and are not intended to be limiting thereof.

EXAMPLES

In the following examples, and throughout this specification, all parts and

percentages are by weight, and all temperatures are in degrees Celsius, unless expressly stated to be otherwise. Where the solids content of a dispersion or solution

is reported, it expresses the weight of solids based on the total weight of the dispersion

or solution, respectively. Where a molecular weight is specified, it is the molecular

weight range ascribed to the product by the commercial supplier, which is identified.

Generally this is believed to be weight average molecular weight.

I. Methods.

A. The Wet Slide Test for Adherence:

The primary functional difference between the compositions of the present

invention and compositions which contain barrier materials alone without a transfer

agent is that the compositions of the present invention will adhere to a wet negatively-

charged surface, such as a wet glass microscope slide but unmodified barrier materials

will not adhere. Therefore, the primary functionality test for compositions of the

present invention formulations is the Wet Slide Test, Protocol CB 01, which may be

used both for initial evaluations of compositions of the present invention and for

stability evaluations.

1. Materials

a. Substrate

Glass microscope slides, such as VWR Cat No 48312-400, approximate

dimensions 1" x 3" x 1.0 mm, are cleaned (even if "pre-cleaned" slides are purchased)

by manually washing for 30 seconds per slide in 2% aqueous sodium lauryl sulfate

(90%) or greater) solution or equivalent, exhaustively rinsing in tap water, followed by

a final rinse in distilled or deionized water, and air drying at room temperature. b. Water

Water for final rinse of substrate (above) and for test is Alhambra (brand)

Distilled Drinking Water (McKesson Water Products Co., Pasadena, CA, 91107

U.S.A) or equivalent.

c. Applicator

Applicator is Longs (brand) Double-Tipped Cotton Swabs (Longs Drug

Stores, Walnut Creek, CA 94596 U.S.A.) or equivalent.

d. Control

Hanson Microcrystalline Wax, Hansonwax code JH 835, Dilco Refining

Division, Eastern Mohair and Trading Company, Inc. 73-35 Grand Avenue, Maspeth,

New York 11378 U.S.A.

2. Procedure

1. The ambient temperature, the temperature of the water, the slide, and the

test product must be 25±5°C.

2. Thoroughly coat the applicator tip with Control by rubbing the applicator

on and in the Control product.

3. Holding the substrate (slide) horizontal, cover the upper surface of the

substrate with water.

4. Wet the applicator and apply the Control to the water-covered surface of

the substrate by rubbing the Control-coated tip of the applicator thereon.

5. If the Control transfers (visual assay) to the slide leaving a hydrophobic

(high contact angle) area on the substrate, then the slide has been improperly cleaned (see Substrate, above). In such case, the whole batch of cleaned slides (Substrate)

should be re-cleaned as provided under Methods (Substrate).

6. If the Control does not produce a hydrophobic area, then test a Test Product

as in steps 1-4 (Procedure) above.

3. Evaluations

Evaluation of performance is by a visual assay. First, observe a substrate

which is covered with water. Note visually the magnitude of the contact angle

between water and the surface (not an edge) of the substrate. Test materials which are

• judged to be effective (a report of +, ++, or +++) will produce a contact angle with

water greater than that produced by water in contact with a cleaned substrate. Test

materials which are ineffective (a report of -) will not deposit material on the substrate

in the test and will not produce an increased contact angle between water and treated

surface.

4. Functionality

- Describes the performance of Control or an ineffective test product.

No test material is deposited on the surface of the substrate (slide) in the test and the

contact angle between water and the substrate is not changed as compared to the

water-coated substrate prior to test.

+ Describes the performance of a marginally effective product. A small

amount of test material is discontinuously deposited on the substrate (slide) in the test

and the contact angle is little increased as compared to the water-coated substrate prior

to test. ++ Describes a product of intermediate effectiveness. An intermediate

amount of test material is deposited on the substrate (slide) in the test and the contact

angle is somewhat increased as compared to the water-coated substrate prior to test.

+++ Describes a highly effective test material. A substantial amount of test

material is continuously deposited on the substrate (slide) in the test and the contact

angle is greatly increased as compared to the water-coated substrate prior to test.

II. Examples:

Example 1.

Polydimethylsiloxanes (PMDS) of various molecular weights, obtained from

United Chemical Technologies, Inc. (UCT), were mixed, using a spatula, with a

transfer agent, hexetidine, in a ratio of 0.1 milliliter of transfer agent (abbreviated Hx)

to 2.0 g of polymer or polymer mixture. Mixtures of polymers are in a ratio of 4 g of

the higher MW polymer plus 1 g of the lower MW polymer. The higher molecular

weight polymers required substantial time and force to produce a homogeneous

mixture. Each of the mixtures described below was then tested in the wet slide test as

indicated below:

Polydimethylsiloxanes :

Cat.No. Viscosity (cs MW Hazard

P-034 0.65 162 Irritant

P-040 50 3,780 None P-042 500 17,250 None

P-044 5000 49,350 None

P-048 100,000 139,000 None

P-049 600,000 260,000 None

P-049.5 1,000,000 308,000 None

P-050 2,500,000 423,000 None

Make the following formulations:

No. Composition Wet Slide Test

1. P-034

P-034, Hx ++

P-040

4. P-040, Hx +++

5. P-042

6. P-042, Hx +++

7. P-044

8. P-044, Hx +++

9. P-048

10. P-048, Hx +++

11. P-048, P-034, Hx

12. P-48, P-040, Hx +++

13. P-048, P-042, Hx +++

14. P-049 15. P-049, Hx +++

16. P-049, P-034, Hx +++

17. P-049, P-040, Hx +++

18. p-049, P-042, Hx

19. P-049.5

20. P-049.5, Hx +++

21. P-049.5, P-034, Hx

22. P-049.5, P-040, Hx +++

23. P-049.5, P-042, Hx +++

24. P-050

25. P-050, Hx +++

Example 2.

100 Grams of UCT PS050 polydimethylsiloxane, approximately 2,500,000

centistokes viscosity was mixed with 6.0 g of hexetidine. Clove oil (0.2 milliliter)

was added for aroma and approximately 200 g of octamethylcyclotetrasiloxane (GE

1173) was added to decrease viscosity and allow thorough mixing. The formulation

was tested as a protective hand and face preparation; users reported good effects. It

was noted that the preparation could be applied to wet skin to moisturize and seal in

moisture. Similar formulations having between half as much volatile silicone diluent

to twice as much volatile silicone diluent had similar attributes but the more dilute

formulations left a thinner coating of silicone on the skin. Example 3.

75 Grams of wax was melted at approximately 85 °C and 3.8 g of hexetidine

was added. Then the mixture was diluted with approximately 150 g of SF 1173

(General Electric octamethylcyclotetrasiloxane). This formulation was tested as is in

the wet slide test (results positive) and as a makeup foundation. It was also further

diluted with up to 450 more grams of volatile silicone diluent. All dilutions gave

similar results, some subjects preferring the less viscous formulations and some

preferring the more viscous formulations. This formulation had exceptional

performance in minimizing imperfections in the skin, especially when used as a make

up foundation. In this mode of use, the skin is first washed thoroughly and then the

makeup foundation preparation is applied liberally to sparingly all over the face. It is

notable that, even when applying the preparation to skin blemishes and lesions which

are oozing tissue fluids, the preparation goes on easily and evenly, adhering uniformly

to damaged and undamaged regions alike. After allowing a few moments for the

foundation to dry, ordinary facial make up is applied in the usual manner. It is notable

that when this formulation is applied to the skin as a foundation, ordinary makeup,

which can often accentuate rather than hide oozing and dry skin blemishes and

lesions, goes evenly and uniformly over healthy and blemished skin alike, evening out

skin tones and hiding blemishes very effectively. It is also noted that when make up

is removed by washing, this make up foundation preparation aids in cleaning the skin. Example 4.

The following skin care formulations were prepared by mixing the ingredients

under the conditions indicated:

Formulation Wax Trans. Agent Diluent (SF 1202) Wet Slide Test

1 33g 1.0ml 66g +++

2 49g 1.5ml 50g +++

3 25g 1.0ml 74g +++

4 30g 1.0ml 63g

5 6.25g 0.25ml 43.5 +++

Numbers 1, 2, and 3 were prepared by melting the wax at approximately 85

°C, adding hexetidine and diluent, and mixing thoroughly. Number 5 is prepared by

heating 25 g of number 3 to melt and diluting with 25 g of diluent, then cooling with

stirring. Number 4 is a medicated formulation containing benzoyl peroxide, a

recognized anti-acne agent. Benzoyl peroxide (BPO) is obtained from UCT as PC

020-KG, a paste which is 50% BPO in polydimethylsiloxane (PDMS). The BPO

paste is first mixed with diluent at approximately 25 °C then warmed to 75 °C in a

water bath, while the wax is melted together with hexetidine at approximately 90 °C.

Then, the wax mixture is poured into the BPO-diluent mixture stirring on the water

bath and the final mixture is cooled while shaking.

Formulations 1, 2, 3, and 5 performed essentially the same as the formulation

described in Example 3. Formulation 4 was cosmetically similar to the above formulations but was effective in one day and even more effective when used daily

over two weeks in controlling acne. While BPO is a recognized anti-acne agent, most

formulations incorporating this ingredient do not provide desirable cosmetic

appearance when in use. Such conventional BPO formulations tend to dry and can

often irritate the skin and often can accentuate rather than hide blemishes and tend to

result in uneven skin tones, even when conventional make up is applied over a BPO

foundation. In contrast, formulation 4 exhibited all the favorable cosmetic attributes

and functionalities of the other formulations (1, 2, 3, and 5 as well as Example 3)

while treating and ameliorating acne lesions with superior efficacy. In short, the

present formulation seems to enhance the activity of BPO, allowing it to work more

quickly, to hide blemishes while it is working, and to allow BPO to be used for many

days continuously for overall superior results.

Example 5.

In this example, BPO is 50% Benzoyl Peroxide in PDMS, UCT # PCO20-KG,

Lot 120715. BPO is a monographed over-the counter (OTC) acne medication which,

heretofore, has not been formulated in really esthetic products. This example, in

which BPO constitutes 10%> of the non-volatile fraction of the product (10%) is the

OTC limit), is prepared as follows:

Dilute 6.7 g of BPO in 68 g of cyclomethicone (GE SF1202,

decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane) and warm to 80 °C

with stirring. Melt 25 g of wax and add 1.7 g of hexetidine. Pour the wax mixture

into the BPO mixture and stir. Dispense into bottles. A different order of addition (mix the BPO with the hexetidine, add melted

wax, and then add the cyclomethicone) gave the same results.

The final composition is 5%> hexetidine, 10%> BPO, in the wax (exclusive of

volatiles), its performance was the same as for formulation number 4 in Example 4

above.

Example 6.

A waterproof sunscreen is prepared as follows:

Dissolve 15 g of UTC PS 050 (2,500,000 cs PDMS) in 100 g of

decamethylcyclotetrasiloxane. Add 5 g of 2-ethylhexyl-trans-methoxy-cinnamate

("Octamethyl Cinnamate," a UV absorber used in sunscreen products) and 1 g of

hexetidine and stir. Observation: it doesn't wash off.

Example 7.

This Example is similar to Example 2 which uses PDMS as the barrier and

Example 3 which uses wax as the barrier. This example uses a mixture of wax and

PDMS as the barrier and is prepared using the following amounts of ingredients and

the following procedure:

16.6 g of PS049.5 (1,000,000 cs PDMS)

16.6 g of Wax

1 g of Hexetidene

66.4 g of solvent GE SF1202 Mix the PDMS with the solvent and warm to about 85 °C; add the wax and

stir, to melt and mix; add the hexetidine and stir; and shake while cooling.

The formulation is superior to both Examples 2 and 3 in that the ratio of the

two distinctly different barrier materials may be varied to produce cosmetic

preparations which deliver a range of skin feel from relatively "hard," with a

preponderance of wax, to supple, with a preponderance of PDMS.

Example 8.

Three formulations are prepared as follows:

A) 2% hexetidine.

Melt 83 grams of wax at 90 °C, add 15 grams of oil and 2 grams of hexetidine,

and mix by stirring.

B) 6% Lecithin, 1% Hexetidine.

Mix 6 grams of lecithin, 100 ml of hexane, and 15 grams of oil by stirring,

then add 1 gram of hexetidine with stirring. Warm just to the boiling point of hexane

and gently evaporate the hexane. Add 78 grams of wax and melt at 75 °C on a water

bath. Mix by stirring.

C) 12% Lecithin

Mix 12 grams of of lecithin, 100 ml of hexane, and 15 grams of oil by

stirring. Warm just to the boiling point of hexane and gently evaporate the hexane.

Add 73 grams of wax and melt at 75 °C on a water bath. Mix by stirring.

Melt A and C on a water bath. Add 50 grams of A to 50 grams of B, and mix

by stirring.

+++ Highly effective, ++ Effective, + Somewhat Effective, - Ineffective.

The lecithin formulations give an exceptional degree of suppleness, and the

lecithin itself may, to some extent, plasticize the skin, this being a natural component

of the skin.

Example 9.

A silicone-based skin formulation is prepared using the following amounts of

ingredients and the following procedure:

33.0 g of PS 050 (2,500,000 cs PDMS),

132 g of GE Octamethylcyclotetrasiloxane, and

1.0 ml of hexetidine,

Heat no higher than 60°C and stir overnight.

This composition passes the wet slide test.

Example 10.

These silicone formulations are prepared using the following amounts of

ingredients and the following procedures: 1. Mix 23.7 g of UCT PS 050 (2,500,000cs PDMS) with

71.1 g of Decamethycyclopentasiloxane (G.E.);

Heat and stir to dissolve (Takes a long time):

Add 1.0 g of hexetidine; and mix well.

Wet glass slide test: +++

2. Melt 40.5 g of Wax, at ca. 85 °C;

Add 4.0 g of Hexetidine, mix well;

Add 40.5 g of Decamethycyclopentasiloxane (G.E.); and

Mix well.

Wet glass slide test: +++

3. Mix 33.2 g of melted formulation no. 2 with

33.2 g of Decame hylcyclopentasiloxane (G.E.);

Mix well.

Wet glass slide test: +++

4. Controls Wet glass slide test:

Wax:

Decamethycyclopentasiloxane (G.E.)

UCT PS 050 (2,500,000cs PDMS)

Note that a control formulation, without transfer agent, did not pass the wet slide test. Example 11.

An athletes foot formulation is prepared using the following amounts of

ingredients and the following procedure;

278 g of wax (75%),

55 g of oil (15%), and

37 g of hexetidine (10%) (50 ml of 90% hexetidine).

Heat to melt wax and mix; and

Dispense into containers.

It is reported that this formulation rapidly treats and cures athletes foot (fungal

infection).

Wax-Based Cream Formulations:

Example 12.

The wax-based hand-cream formulation was prepared by combining 10 grams

of microcrystalline wax, 10 grams of 50% lecithin* dissolved in paraffin oil, 10 grams

of water, 2 grams of isopropyl alcohol, 0.5 grams of hexetidine and 1 gram of

citronella fragrance (Aura Cacia,** 100%) essential oil). The mixture was liquefied by

heating to approx. 90 °C. It was stirred vigorously until the temperature dropped

below 50 °C and the mixture solidified into a formulation which is smooth and creamy

in consistency. In this type of formulation, the ratio of water and wax may be varied

to produce cosmetic preparations which deliver a range of skin feel from relatively

"soft," with a preponderance of water, to 'hard," with a preponderance of wax. Example 13.

The wax-based cream composition, suitable as a base for makeup, was

prepared by combining 10 grams of microcrystalline wax with 4 grams of 50%>

lecithin dissolved in paraffin oil, 2 grams of 50%> beeswax dissolved in paraffin oil, 10

grams of water, 0.5 grams of hexetidine, and 1 gram of orange fragrance (Aura Cacia,

100%) essential oil). The mixture was liquefied by heating to approx. 90°C. It was

stirred vigorously until the temperature dropped below 50 °C and the mixture

solidified into a smooth creamy consistency suitable for mascaras and eye makeup.

Wax 25% to 80%

Lecithin l% to 50%

Water 25% to 50%

* Manufactured by Archer Daniel Midload Co. under trade name of ULTRALEC P,

lot# UF/040

** Manufactured by Aura Cacia, Weaverville, Ca.

Chitosan-Containing Composition:

Example 14.

A composition including de-oiled lecithin is shown in the table below: Components Weight %

Microcrystalline 70

Wax

Paraffme Oil 25 Liquid Lecithin 5

In a typical product preparation, 10 grams of the above formulation is

liquefied by heating to 80-100°C and combined with 10 grams of de-acetylated

chitosan (Aldrich Chemical Co., 1001 West St. Paul Ave., Milwaukee, WI 53233,

catalog no. 44,887-7). The components are mixed until a homogenous paste is

obtained. In a separate container, 100 ml of water containing one g of a chitosan fiber

dispersion is heated to 80 °C and maintained at this temperature. The lecithin/chitosan

paste is then introduced into the warm water and mixed strongly until the paste

transforms into small granules with a typical size of 1 to 2 millimeters. The granules

are filtered and dried in air to yield a free-flowing and non-sticky product. The

product then can be added to a skin care formulation in sufficient quantity (1 to 90

wt.%, preferably 5 to 75 wt.%, more preferably 10 to 50 wt.%) to assure transfer of

the formulation onto the animal's skin. In modification to this approach, the

lecithin/chitosan paste can be extruded into cold water resulting in the formation of

rods or pellets of any desired size and dimensions. Obviously, numerous modifications and variations of the present invention are

possible in light of the above teachings. It is therefore to be understood that, within

the scope of the appended claims, the invention may be practiced otherwise than as

specifically described herein.

All patents and other references mentioned above are incorporated in full

herein by this reference, the same as if set forth at length.

Claims

WHAT IS CLAIMED AS NEW AND DESIRED TO BE SECURED BYLETTERS PATENT OF THE UNITED STATES IS:

1. A composition comprising

(a) 0.25 to 25 wt.%, based on the total weight of (a) and (b), of one or more

transfer agents; and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of one or more

barrier materials.

2. A composition, comprising:

barrier materials; and

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b'"), of

at least one skin care active agent,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

3. The composition of Claim 2, wherein said skin care active agent is selected

from the group consisting of Acetic Acid

Aclometasone Dipropionate

Acyclovir

Alclometasone Dipropionate

Aluminum Chlorhydrate

Aluminum Chlorhydroxide

Aluminum Chloride Hexahydrate

Amcinonide

Aminobenzoate Potassium

Ammonium Lactate

Ammonium Mercury

Amphotericin B

Anthralin

Antimicrobial Agents

Bacitracin

Balsam Pern

Benzocaine

Benzoin Compoundecylenate

Benzoyl Peroxide (BPO)

Beta-Carotene

Betamethasone Acetate

Betamethasone Dipropionate

Betamethasone Sodium Phosphate Betamethasone Valerate

Butaconazole Nitrate

Butamben Picrate

Canthardin

Carbol Fuchsin

Castor Oil

Cetylpyridinium Chloride

Chloramphenicol

Chlorcyclizine

Chlorhexidine

Chlorhexidine Acetate

Chlorhexidine Gluconate

Chloroxine

Chloroxynol

Ciclopirox Olamine

Clindamycin HC1

Clioquinol

Clobetasol Propionate

Clocortolone Pivalate

Clotrimazole

Coal Tar

Collagenase

Cortisone Cortisone Acetate

Crotamiton

Cyclopentolate HC1

Dapsone

Desonide

Desoxymetasone

Desoxyribonuclease

Dexamethasone

Dexamethasone Acetate

Dexamethasone Sodium Phosphate

Dibucaine

Dichloroacetic Acid

Dichlorophene

Diflorasone Diacetate

Diperodon

Econazole Nitrate

Ephedrine HC1

Erythromycin

Estradiol

Etretinate

Fibrinolysin

Flucinolone

Flucinolone Acetonide Fluocinonide

Fluorouracil

Fluradrenolone

Flurandrenolide

Fluticasone Propionate

Formaldehyde

Gentamycin Sulfate

Gramicid

Griseofulvin

Guaifenesin

Halcinonide

Halobetasol Propionate

Haloprogin

Hexachlorophene

Hexetadine

Hyaluronidase

Hydrocodone

Hydrocortisone

Hydrocortisone Acetate

Hydrocortisone Butyrate

Hydrocortisone Sodium Phosphate

Hydrocortisone Sodium Succinate

Hydrocortisone Valerate Hydroquinone

Hydroxyzine HC1

Hydroxyzine Pamoate

Iodine

Iodochlorhydrocodone

Iodoquinol

Isotretinoin

Ketoconazole

Lactic Acid

Lecithin

Lidocaine Hydrochloride

Lindane

Mafenide Acetate

Meclocycline Sulfosalicylate

Methoxsalen

Methylprednisone

Methylprednisone Acetate

Methylprednisone Sodium Succinate

Metronidazole

Miconazole Nitrate

Minoxidil

Mometasone Furoate

Monobenzone Mupriocin

Naftifine HC1

Neomycin Sulfate

Nitrofurazone

Nystatin

Octyl Methoxycinnamate

Oxybenzone

Oxyquinoline Sulfate

Papain

para- Aminobenzoic Acid

Permethrin

Phentermine HC1

Podophylum

Polymyxin B Sulfate

Potassium Iodide

Pramoxine HC1

Prednicarbate

Prednisolone Sodium Phosphate

Prednisone

Pseudoephedrine

Pyrogallic Acid

Retinoic Acid

Retinol Salicylic Acid

S aluminum Acid

Scarlet Red

Selenium Sulfide

Silver Nitrate

Silver Sulfadiazine

Sodium Sulfacetimide

Sodium Thiosulfate

Streptokinase

Sulconazole

Sulconazole Nitrate

Sulfabenzamide

Sulfacetamide

Sulfanilamide

Sulfathiazole

Sulfur

Sunscreen Agents

Sutilains

Terconazole

Tetracaine

Tetracycline

Tretinoin

Triacetin Triamcinolone

Triamcinolone Acetonide

Triamcinolone Diacetate

Trimeprazine Tartrate

Trioxsalen

Triple Dye

Trypsin

Undecylenic Acid

Urea

Vitamins (all)

Zinc Oxide

Zinc Undecylenate

and other agents known in the art to have medical, cosmetic, or other effects on the

skin.

4. A method for forming a protective barrier on skin, said method comprising

applying an effective amount of a composition to skin, said composition comprising:

and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of a barrier

material.

5. A method for cleaning and removing contaminants from the skin while forming a protective barrier on skin, said method comprising applying an

effective amount of a composition to skin, said composition comprising:

(a) 0.25 to 25 wt.%>, based on the total weight of (a) and (b), of a transfer

agent; and

(b) 75 to 99.75 wt%, based on the total weight of (a) and (b), of a barrier

material.

6. A method for applying a skin care agent to skin, said method comprising

(a') 65 to 99.75 wt.%, based on the total weight of (a') and (b'), of one or

more barrier materials; and

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b"'), of

at least one skin care agent,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%, based on the total weight of said composition.

7. A method for cleaning and removing contaminants from the skin while

amount of composition to skin, said composition comprising: (a') 65 to 99.75 wt.%, based on the total weight of (a') and (b'), of one or more barrier materials; and

said mixture comprising:

(b' 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b'"), of

at least one skin care agent, provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

8. A composition which comprises:

material;

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water.

9. The composition of claim 8, which comprises:

material;

(3) 30 to 40 wt.%, based on the total weight of (1), (2), and (3), of water.

10. A method for forming a protective barrier on skin, said method

comprising applying an effective amount of a composition to skin, said composition

comprising:

material;

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water.

11. A method for cleaning and removing contaminants from the skin while

performing a protective barrier on skin, said method comprising applying an effective

amount of a composition to skin, said composition comprising:

(1) 25 to 80 wt.%, based on the total weight of (1), (2), and (3), of a barrier

material;

(3) 20 to 50 wt.%), based on the total weight of (1), (2), and (3), of water.

12. The method of Claim 10 or 11 , wherein said composition comprises:

material;

(3) 30 to 40 wt.%, based on the total weight of (1), (2), and (3), of water.

13. A composition which comprises: (i) 1 to 30 wt.%), based on the total weight of (i), (ii), and (iii), of lecithin;

material; and

14. The composition of Claim 13, which comprises:

material; and

15. A method for forming a protective barrier on skin, said method

comprising:

(i) 1 to 30 wt.%, based on the total weight of (i), (ii), and (iii), of lecithin;

material; and

16. A method for cleaning and removing contaminants from the skin while

forming a protective barrier on skin, said method comprising applying an effective

amount of a composition to skin, said composition comprising:

(i) 1 to 30 wt.%), based on the total weight of (i), (ii), and (iii), of lecithin; (ii) 10 to 30 wt.%), based on the total weight of (i), (ii), and (iii), of a barrier

material; and

17. The method of Claim 15 or 16, wherein said composition comprises:

(i) 5 to 25 wt.%, based on the total weight of (i), (ii), and (iii), of lecithin;

material; and

18. A method for forming a hydrophobic barrier on a surface, comprising

applying to said surface an effective amount of a composition comprising:

(a) 0.25 to 25 wt.%, based on the total weight of (a) and (b), of one or more

transfer agents; and

(b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of one or more

barrier materials.

19. A method for cleaning and removing contaminants from a surface while

forming a hydrophobic barrier on a surface, comprising applying to said surface an

effective amount of a composition comprising:

(a) 0.25 to 25 wt.%>, based on the total weight of (a) and (b), of one or more

transfer agents; and (b) 75 to 99.75 wt.%, based on the total weight of (a) and (b), of one or more

barrier materials.

20. The method of Claim 18 or 19, wherein said surface is selected from the

group consisting of molds, ship hulls, leather, automobile surfaces, wood, metal,

painted surfaces, floors, walls, billboards, train cars, paper, cardboard, pots, pans,

cooking utensils, glass, china, plant foliage, polymers, plastics, fiberglass, fabrics,

resins, composites including carbon fiber and graphitic materials, and mineral

substrates.

21. A method for forming a hydrophobic barrier on a surface, comprising

applying to said surface an effective amount of a composition, comprising:

(a') 65 to 99.75 wt.%, based on the total weight of (a') and (b')- of one or more

barrier materials; and

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b"'), of

at least one active agent,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

22. A method for cleaning and removing contaminants from a surface while

effective amount of a composition, comprising:

barrier materials; and

said mixture comprising:

(b") 0.25 to 99.99 wt.%, based on the total weight of (b") and (b'"), of

one or more transfer agents; and

(b'") 0.01 to 99.75 wt.%, based on the total weight of (b") and (b'"), of

at least one active agent,

provided said transfer agent is present in said composition in an amount of at

least 0.25 wt.%>, based on the total weight of said composition.

23. The method of Claim 21 or 22, wherein said surface is selected from the

resins, composites including carbon fiber and graphitic materials, and mineral

substrates.