`4,741,855
`[11] Patent Number:
`Umted States P31181113
`Grote et al.
`[45] Date of Patent:
`May 3, 1988
`
`
`[19]
`
`.
`
`[54] SHAMPOO COMPOSITIONS
`_
`_
`,
`Inventors: Mark B. Grate, Cmcmnatx; Glen D-
`Russell, Middletown, both of Ohio
`'
`[73] Assignw The ¥’r0ct_er & ‘Gamble Company.
`Cincinnati, Ohio
`[21] Am‘ N°" Wm
`22
`F1 d:
`J 1.31 1987
`[
`]
`I 6
`u
`’
`R 1 ted U.S. A 1'
`ti D ta
`e a
`W lea on
`a
`glontiinuatiroinhof Ser. No._795,t285,_Nov1.15, 19:5, ab§n-
`t
`-
`,
`-
`.
`.
`6;’(')‘§89f:1o::/. 9:S138§’°:b;:]":o::’e':i1n Pa
`O
`er
`°
`Int. CL4 .......................
`075'
`20;
`c11D 9/36;’c11D 17/08
`lLS.(H. ................................. ..2S2/142;252/891;
`252/173; 252/174.15; 252/312; 252/546;
`[
`13;
`[58] Field of Search ................. .. 424/70, 73; 252/89,],
`252/142, 174.15, 312, 546, 547, 548, DIG. 5,
`DIG. 13
`
`[75]
`
`[63]
`
`52
`
`155]
`
`6/1984 Bolich, Jr. ......................... .. 252/547
`4,452,732
`4,470,982 9/1984 Winkle: ........
`424/245
`
`4,479,893 10/1984 Hirota et al.
`.
`252/542
`4,559,227 12/1985 Chandra ................................ 424/70
`FOREIGN PATENT DOCUMENTS
`_
`_
`849433
`9/1960 United Kingdom .
`OTHER PUBLICATIONS
`Bennett, H., Editor, 1974 Chemical Formulary, vol.
`XVIII’ 13- 157-
`Ash et al, 1980, A Formulary of Detergents & Other
`Cleaning Agents’ p_ 76_
`.
`Il;ler11;1gtt, H., 1971, The Chemical Formulary, vol. XVI,
`McCutcheon’s Deterggnts & Emulsifiers, North Amefi-
`can Edition, 1973, pp. 238 & 240.
`_
`_
`_
`.
`P’""‘"3’ E«W"'"e’—1?°m11S Albrecht
`Attorney, Agent, 07' Fzrm-—R1chard Wlttfig Jack D.
`Schaeffef: 130118135 C M0111
`[57]
`ABSTRACT
`.
`.
`.
`.
`Shampoos are disclosed Wh1Cl'l comprise a synthetic
`surfactant, an insoluble, non-volatile silicone, a suspend-
`ing agent and watefr. Shuitable sluspelnding agents incllude
`ong c ain esters 0 et y ene g yco , esters o ong c ain
`.
`.
`.
`.
`fatty acids, long chain amine oxides among many oth-
`CI‘S.
`
`9 Claims, No Drawings
`
`.
`R°f°"°“°°5 Clted
`U_5_ PATENT DOCUMENTS
`1
`3
`8 G
`................................... ..
`2,8 6,
`lggojfo 42336 Aging ...__
`.._H
`3,957,970
`5/1976 Korkis ..... .
`..... 424/70
`3,964,500 6/1976 Drakoff
`......... .. I32/7
`4,364,837 12/1982 Pader .................................. 252/173
`
`9
`
`
`
`UN T. *'.V*'.R *'.X -I
`
`-% T105
`
`UN T.+'.V*'.R VS. PQOCTOQ & GAMBL
`
`000001
`
`IIPR20l3-0050
`
`000001
`
`UNILEVER EXHIBIT 1053
`UNILEVER VS. PROCTOR & GAMBLE
`IPR2013-00509
`
`
`
`4,741,855
`
`1
`
`SHAMPOO COMPOSITIONS
`
`CROSS REFERENCE TO RELATED
`APPLICATION
`
`2
`product. One problem is that of keeping a dispersed,
`insoluble silicone material suspended and the total prod-
`uct stable. A variety of materials have been included in
`silicone containing shampoos for purposes of thickening
`and stabilization but totally satisfactory solutions are
`lacking. It has been surprisingly found that certain long
`chain acyl derivatives and certain other long chain
`derivatives can provide stabilization without interfering
`unduly with deposit of the silicone material onto the
`hair and other shampoo functions.
`It is an object of the present invention to provide a
`stable silicone containing conditioning shampoo.
`It is a further object of the present invention to pro-
`vide silicone shampoo compositions containing certain
`long chain derivatives.
`These and other objects will become readily apparent
`from the detailed description which follows.
`Unless otherwise indicated, all percentages and ratios
`herein are by weight.
`
`SUMMARY OF THE INVENTION
`
`The present invention relates to shampoo composi-
`tions comprising from about 5% to about 70% of a
`synthetic surfactant, about 0.01% to about 10.0% of an
`insoluble, non-volatile silicone, about 0.5% to about
`5.0% of a certain long chain derivative and water.
`These as well as optional components are described in
`detail below.
`
`DETAILED DESCRIPTION
`
`The essential components of the present invention are
`given in the following paragraphs.
`Surfactant
`
`An essential component of the present compositions
`is a surfactant. The surfactant, which may be selected
`from any of a wide variety of synthetic anionic, ampho-
`teric, zwitterionic and nonionic surfactants, is present at
`a level of from about 5% to about 70%, preferably from
`about 10% to about 30%, most preferably from about
`10% to about 22%.
`
`Synthetic anionic surfactants can be exemplified by
`the alkali metal salts of organic sulfuric reaction prod-
`ucts having in their molecular structure an alkyl radical
`containing from 8-22 carbon atoms and a sulfonic acid
`or sulfuric acid ester radical (included in the term alkyl
`is the alkyl portion of higher acyl radicals). Preferred
`are the sodium, ammonium, potassium or triethanol-
`amine alkyl sulfates, especially those obtained by sulfat-
`ing the higher alcohols (C3—C1g carbon atoms), sodium
`coconut oil fatty acid monoglyceride sulfates and sulfo-
`nates; sodium or potassium salts of sulfuric acid esters of
`the reaction product of 1 mole of a higher fatty alcohol
`(e.g., tallow or coconut oil alcohols) and 1 to 12 moles
`of ethylene oxide; sodium or potassium salts of alkyl
`phenol ethylene oxide ether sulfate with l to 10 units of
`ethylene oxide per molecule and in which the alkyl
`radicals contain from 8 to 12, carbon atoms, sodium
`alkyl glyceryl ether sulfonates; the reaction product of
`fatty acids having from 10 to 22 carbon atoms esterified
`with isethionic acid and neutralized with sodium hy-
`droxide; water soluble salts of condensation products of
`fatty acids with sarcosine; and other known in the art.
`Zwitterionic surfactants can be exemplified by those
`which can be broadly described as derivatives of ali-
`phatic quaternary ammonium, phosphonium, and sulfo-
`nium compounds, in which the aliphatic radicals can be
`
`This is a continuation of application Ser. No. 795,285,
`filed on Nov. 5, 1985, now abandoned, which is a con-
`tinuation-in-part of our copending application Ser. No
`670,189, filed Nov. 9, 1984, now abandoned.
`
`TECHNICAL FIELD
`
`invention is related to conditioning
`The present
`shampoos which have a dispersed, non-volatile silicone
`phase and are stabilized through the use of certain long
`chain materials.
`
`BACKGROUND OF THE INVENTION
`
`10
`
`15
`
`20
`
`25
`
`Human hair becomes soiled due to its contact with
`the surrounding atmosphere and, to a greater extent,
`from sebum secreted by the head. The build-up of the
`sebum causes the hair to have a dirty feel and an unat-
`tractive appearance. The soiling of the hair necessitates
`it being shampooed with frequent regularity.
`Shampooing the hair cleans by removing excess soil
`and sebum. However, the shampooing process has dis-
`advantages in that the hair is left in a wet,tangled and
`generally unmanageable state. A variety of approaches
`have been developed to alleviate the after-shampoo
`problems. These range from the inclusion of hair condi-
`tioning aids in shampoos to post-shampoo application of 30
`hair conditioners, i.e., hair rinses. Hair rinses typically
`work by depositing a polymeric film or other material
`onto the hair. However, such solutions to a very preva-
`lent problem have not been fully satisfactory. For one
`thing, hair rinses are generally liquid in nature and must
`be applied in a separate step following the shampooing,
`left on the hair for a length of time, and rinsed with
`fresh water. This, of course, is time consuming and is
`not convenient.
`While shampoos have been disclosed which contain
`conditioning aids, they have not been totally satisfac-
`tory for a variety of reasons. One problem relates to
`compatibility problems between good cleaning anionic
`surfactants and the fatty cationic agents which are good
`conditioning agents. This caused other surfactants such
`as nonionics, amphoterics and zwitterionics to be exam-
`ined by workers in the field. Many of these efforts are
`reflected in patents issued in the conditioning shampoo
`area. See for example U.S. Pat. No. 3,849,348, Nov. 19,
`1974 to Hewitt; U.S. Pat. No. 3,990,991, Nov. 9, 1961 to
`Gerstein; and U.S. Pat. No. 3,822,312, July 2, 1974 to
`Sato‘.
`
`35
`
`45
`
`50
`
`The use of these other surfactants solved many of the
`compatibility problems but still did not provide com-
`plete answers in all areas. For instance cationic condi-
`tioners may not deliver the desired level of softness
`desired by users. Materials which can provide increased
`softness are silicones, both those which are soluble as
`well as insoluble in the shampoo matrix.
`Silicones in shampoo compositions have been dis-
`closed in a number of different publications. Such publi-
`cations include U.S. Pat. No. 2,826,551, Mar. 11, 1958 to
`Geen; U.S. Pat. No. 3,964,500, June 22, 1976 to Drakoff;
`U.S. Pat. No. 4,364,837, Dec. 21, 1982 to Pader; and
`British Pat. No. 849,433, Sept. 28, 1960 to Woolston.
`While these patents disclose silicone containing compo-
`sitions, they also do not provide answers to all of the
`problems encountered in making a totally satisfactory
`
`55
`
`60
`
`65
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`000002
`
`
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`4,741,855
`
`3
`straight chain or branched, and wherein one of the
`aliphatic substituents contains from about 8 to 18 carbon
`atoms and one contains an anionic water-solubilizing
`group, e.g., carboxyl, sulfonate, sulfate, phosphate, or
`phosphonate. A general formula for these compounds 5
`1s:
`
`4
`those which can be broadly described as derivatives of
`aliphatic secondary and tertiary amines in which the
`aliphatic radical can be straight chain or branched and
`wherein one of the aliphatic substituents contains from
`about 8 to about 18 carbon atoms and one contains an
`anionic water solubilizing group, e.g., carboxy, sulfo-
`nate, sulfate, phosphate, or phosphonate. Examples of
`compounds falling within this definition are sodium
`3-dodecylaminopropionate,
`sodium 3-dodecylamino-
`propane sulfonate, N-alkyltaurines such as the one pre-
`pared by reacting dodecylamine with sodium isethion-
`ate according to the teaching of U.S. Pat. No. 2,658,072,
`N-higher alkyl aspartic acids such as those produced
`according to the teaching of U.S. Pat. No. 2,438,091,
`and the products sold under the trade name “Miranol”
`and described in U.S. Pat. No. 2,528,378.
`Nonionic surfactants, which are preferably used in
`combination with an anionic, amphoteric or zwitter-
`ionic surfactant, can be broadly defined as compounds
`produced by the condensation of alkylene oxide groups
`(hydrophilic in nature) with an organic hydrophobic
`compound, which may be aliphatic or alkyl aromatic in
`nature. Examples of preferred classes of nonionic sur-
`factants are:
`l. The polyethylene oxide condensates of alkyl phe-
`nols, e.g., the condensation products of alkyl phenols
`having an alkyl group containing from about 6 to 12
`carbon atoms in either a straight chain or branched
`chain configuration, with ethylene oxide, the said ethyl-
`ene oxide being present in amounts equal to 10 to 60
`moles of ethylene oxide per mole of alkyl phenol. The
`alkyl substituent in such compounds may be derived
`from polymerized propylene, diisobutylene, octane, or
`nonane, for example.
`2. Those derived from the condensation of ethylene
`oxide with the product resulting from the reaction of
`propylene oxide and ethylene diamine products which
`may be varied in composition depending upon the bal-
`ance between the hydrophobic and hydrophilic ele-
`ments which is desired. For example, compounds con-
`taining from about 40% to about 80% polyoxyethylene
`by weight and having a molecular weight of from about
`5,000 to about 11,000 resulting from the reaction of
`ethylene oxide groups with a hydrophobic base consti-
`tuted of the reaction product of ethylene diamine and
`excess propylene oxide, said base having a molecular
`weight of the order of 2,500 to 3,000, are satisfactory.
`3. The condensation product of aliphatic alcohols
`having from 8 to 18 carbon atoms, in either straight
`chain or branched chain configuration, with ethylene
`oxide, e.g., a coconut alcohol ethylene oxide condensate
`having from 10 to 30 moles of ethylene oxide per mole
`of coconut alcohol, the coconut alcohol fraction having
`from 10 to 14 carbon atoms.
`4. Long chain tertiary amine oxides corresponding to
`the following general formula:
`
`R1RzR3N
`
`0
`
`wherein R1 contains an alkyl, alkenyl or monohydroxy
`alkyl radical of from about 8 to about 18 carbon atoms,
`from 0 to about 10 ethylene oxide moieties, and from 0
`to 1 glyceryl moiety, and R2 and R3 contain from 1 to
`about 3 carbon atoms and from 0 to about 1 hydroxy
`group, e.g., methyl, ethyl, propyl, hydroxy ethyl, or
`hydroxy propyl radicals. The arrow in the formula is a
`conventional representation of a semipolar bond. Exam-
`ples of amine oxides suitable for use in this invention
`
`(R3) x
`
`R2 Y(+> CH2 R4
`
`z<->
`
`10
`
`15
`
`25
`
`30
`
`35
`
`40
`
`wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl
`radical of from about 8 to about 18 carbon atoms, from
`0 to about 10 ethylene oxide moieties and from 0 to l
`glyceryl moiety; Y is selected from the group consisting
`of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl
`or monohydroxyalkyl group containing 1 to about 3
`carbon atoms; X is 1 when Y is a sulfur atom and 2 when
`Y is a nitrogen or phosphorus atom; R4 is an alkylene or
`hydroxyalkylene of from 1 to about 4 carbon atoms and 20
`Z is a radical selected from the group consisting of
`carboxylate, sulfonate, sulfate, phosphonate, and phos-
`phate groups.
`Examples include:
`4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-
`butane-1-carboxylate;
`5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxy-
`pentane-1-sulfate;
`3-[P,P-diethyl-P-3,6,9-trioxatetradexocylphosphonio]-
`2-hydroxypropane-1-phosphate;
`3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropylam-
`monio]-propane-l-phosphonate;
`3-(N,N-dimethyl-N-hexadecylammonio)propane- l-sul-
`fonate;
`3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-
`propane-1-sulfonate;
`4-[N,N-di(2-hydroxyethyl)-N-(2-hydroxydodecyl)am-
`monio]-butane-1-carboxylate;
`3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-
`propane-1-phosphate;
`3-[P,P-dimethyl-P-dodecylphosphonio]-propane- 1-
`phosphonate; and
`5-[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-
`hydroxypentane-l-sulfate.
`Other zwitterionics such as betaines are also useful in 45
`the present
`invention. Examples of betaines useful
`herein include the high alkyl betaines such as coco
`dimethyl carboxymethyl betaine, lauryl dimethyl car-
`boxymethyl betaine,
`lauryl dimethyl alpha-carboxy-
`ethyl betaine, cetyl dimethyl carboxymethyl betaine,
`lauryl bis-(2-hydroxy-ethyl)carboxy methyl betaine,
`stearyl bis-(2-hydroxy-propyl)carboxymethy1 betaine,
`oleyl dimethyl gamma-carboxypropyl betaine,
`lauryl
`bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, etc.
`The sulfobetaines may be represented by coco dimethyl
`sulfopropyl betaine, stearyl dimethyl sulfopropyl beta-
`ine,
`lauryl dimethyl sulfoethyl betaine,
`lauryl bis-(2-
`hydroxy-ethyl)sulfopropyl betaine and the like; amido
`betaines
`and
`amidosulfobetaines, wherein
`the
`RCONH(CH2)3 radical is attached to the nitrogen atom
`of the betaine are also useful in this invention. The
`amido betaines are preferred for use in some of the
`compositions of this invention. A particularly preferred
`composition utilizes an amido betaine, a quaternary
`compound, a silicone, a suspending agent and has a pH
`of from about 2 to about 4.
`Examples of amphoteric surfactants which can be
`used in the compositions of the present invention are
`
`50
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`
`60
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`65
`
`000003
`
`000003
`
`
`
`4,741,855
`
`5
`oleyldi(2-
`oxide,
`dimethyl-dodecylamine
`include
`hydroxyethyl)amine oxide, dimethyloctylamine oxide,
`dimethyl-decylamine oxide, dimethyltetradecylamine
`oxide, 3,6,9-trioxaheptadecyldiethylamine oxide, di(2-
`hydroxyethyl)-tetradecylamine oxide, 2-dode-coxye-
`thyldimethylamine
`oxide,
`3-dodecoxy-2-hydroxy-
`propyldi(3-hydroxypropyl)amine oxide, dimethylhex-
`adecylamine oxide.
`5. Long chain tertiary phosphine oxides correspond-
`ing to the following general formula:
`RR'R"P
`0
`
`wherein R contains an alkyl, alkenyl or monohydroxy-
`alkyl radical ranging from 8 to 18 carbon atoms in chain
`length, from 0 to about 10 ethylene oxide moieties and
`from 0 to l glyceryl moiety and R’ and R” are each
`alkyl or monohydroxyalkyl groups containing from 1 to
`3 carbon atoms. The arrow in the formula is a conven-
`tional representation of a semipolar bond. Examples of
`suitable phosphine oxides are: dodecyldimethylphos-
`phine oxide,
`tetradecyldimethylphosphine oxide,
`tet-
`radecylmethylethylphosphine
`oxide,
`3,6,9,-trioxaoc-
`tadecyldimethylphosphine oxide, cetyldimethylphos-
`phine oxide, 3-dodecoxy-2-hydroxypropyldi(2-hydrox-
`yethyl)phosphine oxide, stearyldimethylphosphine ox-
`ide, cetylethylpropylphosphine oxide, oleyldiethyl-
`phosphine oxide, dodecyldiethylphosphine oxide, tet-
`radecyldiethylphosphine oxide, dodecyldipropylphos-
`phine oxide, dodecyldi(hydroxymethy1)phosphine ox-
`ide, dodecyldi(2-hydroxyethyl)phosphine oxide,
`tet-
`radecylmethyl-2-hydroxypropylphosphine oxide, oleyl-
`dimethylphosphine oxide, 2-hydroxydodecyldimethyl-
`phosphine oxide.
`6. Long chain dialkyl sulfoxides containing one short
`chain alkyl or hydroxy alkyl radical of l to about 3
`carbon atoms (usually methyl) and one long hydropho-
`bic chain which contain alkyl, alkenyl, hydroxy alkyl,
`or keto alkyl radicals containing from about 8 to about
`20 carbon atoms, from 0 to about 10 ethylene oxide
`moieties and from 0 to 1 glyceryl moiety. Examples
`include: octadecyl methyl
`sulfoxide, 2-ketotridecyl
`methyl sulfoxide, 3,6,9,-trioxaoctadecyl 2-hydroxyethyl
`sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxy-
`propyl
`sulfoxide,
`tetradecyl methyl
`sulfoxide,
`3-
`methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl
`methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl
`sulfoxide.
`
`Many additional nonsoap surfactants are described in
`McCUTCHEON’S, DETERGENTS AND EMULSI-
`FIERS, 1979 ANNUAL, published by Allured Publish-
`ing Corporation, which is incorporated herein by refer-
`ence.
`
`The above-mentioned surfactants can be used alone
`or in combination in the shampoo compositions of the
`present invention. The anionic surfactants, particularly
`the alkyl sulfates,
`the ethoxylated alkyl sulfates and
`mixtures thereof are preferred for use herein as well as
`the amido betaines.
`
`-
`
`6
`tions. The dispersed silicone particles should also be
`insoluble in the shampoo matrix. This is the meaning of
`“insoluble” as used hereinbefore and hereinafter.
`The essentially non-volatile polyalkyl siloxane fluids
`that may be used include, for example, polydimethyl
`siloxanes with viscosities ranging from about 5 to
`600,000 centistokes at 25° C. These siloxanes are avail-
`
`10
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`30
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`35
`
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`
`50
`
`able, for example, from the General Electric Company
`as the Viscasil series and from Dow Corning as the
`Dow Corning 200 series. The viscosity can be measured
`by means of a glass capillary viscometer as set forth in
`Dow Corning Corporate Test Method CTM0004, July
`20, 1970. Preferably the viscosity ranges from about 350
`centistokes to about 100,000 centistokes.
`The essentially non-volatile polyalkylaryl siloxane
`fluids that may be used include, for example, polyme-
`thylphenylsiloxanes having viscosities of about 15 to
`30,000 centistokes at 25° C. These siloxanes are avail-
`able, for example, from the General Electric Company
`as SF 1075 methyl phenyl fluid or from Dow Corning
`as 556 Cosmetic Grade Fluid.
`
`The essentially non-volatile polyether sioxane co-
`polymer that may be used is, for example, a polypropyl-
`ene oxide modified dimethylpolysiloxane (e.g., Dow
`Corning DC-1248) although ethylene oxide or mixtures
`of ethylene oxide and propylene oxide may also be used.
`References disclosing suitable silicone fluids include
`the previously mentioned U.S. Pat. No. 2,826,551 to
`Geen; US. Pat. No. 3,964,500, June 22, 1976 to Drakoff;
`U.S. Pat. No. 4,364,837 to Pader and British Pat. No.
`849,433 to Woolston. All of these patents are incorpo-
`rated herein by reference. Also incorporated herein by
`reference is Silicon Compounds distributed by Petrarch
`Systems, Inc., 1984. This reference provides a very
`good listing of suitable silicone materials.
`Another silicone material found especially useful in
`the present compositions to provide good dry combing
`is a silicone gum. Silicone gums described by Petrarch
`and others including U.S. Pat. No. 4,152,416, May 1,
`1979 to Spitzer, et al. and Noll, Walter, Chemistry and
`Technolog of Silicones, New York: Academic Press
`1968. Also describing silicone gums are General Elec-
`tric Silicone Rubber Product Data Sheets SE 30, SE 33,
`SE 54 and SE 76. All of these described references are
`incorporated herein by reference. “Silicone gum” mate-
`rials denote high molecular weight polydiorganosilox-
`anes having a mass molecular weight of from about
`200,000 to about 1,000,000. Specific examples include
`polydimethylsiloxane, (polydimethylsiloxane) (methyl-
`vinylsiloxane) copolymer, po1y(dimethylsiloxane) (di-
`phenyl) (methylvinylsiloxane) copolymer and mixtures
`thereof.
`
`55
`
`Long Chain Derivative Suspending Agent
`
`Non-Volatile Silicone Fluid
`
`Silicone fluids are a suitable non-volatile silicone that
`may be used in the present compositions.
`The non-volatile silicone fluid may be either a polyal-
`kyl siloxane, a polyaryl siloxane, a polyalkylaryl silox-
`ane or a polyether siloxane copolymer and is present at
`a level of from about 0.1% to about 10.00% preferably
`from about 0.5% to about 5.0%. Mixtures of these fluids
`may also be used and are preferred in certain execu-
`
`65
`
`The suspending agent useful in the present composi-
`tions can be any of several long chain acyl derivative
`materials or mixtures of such materials. Included are
`ethylene glycol esters of fatty acids having from about
`16 to about 22 carbon atoms. Preferred are the ethylene
`glycol stearates, both mono and distearate, but particu-
`larly the distearate containing less than about 7% of the
`mono stearate. Other suspending agents found useful
`are alkanol amides of fatty acids, having from about 16
`to about 22 carbon atoms, preferably about 16 to 18
`carbon atoms. Preferred alkanol amides are stearic
`monoethanolamide,
`stearic diethanolamide,
`stearic
`monoisopropanolamide and stearic monoethanolamide
`
`000004
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`4,741,855
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`7
`stearate. Other long chain acyl derivatives include long
`chain esters of long chain fatty acids (e.g., stearyl stea-
`rate, cetyl palmitate, etc.); glyceryl esters (e.g., glyceryl
`distearate) and long chain esters of long chain alkanol
`amides (e.g., stearamide DEA distearate, stearamide
`MEA stearate).
`Still other suitable suspending agents are alkyl (C15.
`22) dimethyl amine oxides such as stearyl dimethyl
`amine oxide. If the compositions contain an amine oxide
`or a long chain acyl derivative as a surfactant the sus-
`pending function could also be provided and additional
`suspending agent may not be needed if the level of those
`materials are at least the minimum level given below.
`The suspending agent is present at a level of from
`about 0.50% to about 5.0%, preferably from about
`0.5% to about 3.0%. The suspending agent serves to
`assist in suspending the silicone material and may give
`pearlescence to the product. Mixtures of suspending
`agents are also suitable for use in the compositions of 20
`this invention.
`
`5
`
`10
`
`15
`
`Water
`
`Water is the last essential component of the present
`invention and forms the remainder of the composition.
`It is generally present at a level of from about 20% to
`about 95%, preferably from about 60% to about 85%.
`
`Optional Components
`The shampoos herein can contain a variety of non-
`essential optional components suitable for rendering
`such compositions more acceptable. Such conventional
`optional ingredients are well known to those skilled in
`the art, e.g., preservatives such as benzyl alcohol,
`methyl paraben, propyl paraben and imidazolidinyl
`urea; cationic surfactants such as cetyl trimethyl ammo-
`nium chloride,
`lauryl trimethyl ammonium chloride,
`tricetyl methyl ammonium chloride, stearyldimethyl
`benzyl ammonium chloride, and di(partially hydroge-
`nated tallow)dimethyla1nmonium chloride; thickeners
`and viscosity modifiers such as a diethanolamide of a
`long chain fatty acid (e.g., PEG 3 lauramide), block
`polymers of ethylene oxide and propylene oxide such as
`Pluronic F88 offered by BASF Wyandotte, sodium
`chloride, sodium sulfate, polyvinyl alcohol, and ethyl
`alcohol; pH adjusting agents such as citric acid, succinic
`acid, phosphoric acid, sodium hydroxide, sodium car-
`bonate, etc.; perfumes; dyes; and, sequestering agents
`such as disodium ethylenediamine tetraacetate. Such
`agents generally are used individually at a level of from
`about 0.01% to about 10%, preferably from about 0.5%
`to about 5.0% by weight of the composition.
`The pH of the present compositions is not critical and
`may be in the range of from 2 to about 10. However, as
`set forth earlier cerain zwitterionic/quaternary compo-
`sitions preferably have pH’s of from about 2 to about 4.
`METHOD OF MANUFACTURE
`
`25
`
`30
`
`35
`
`45
`
`50
`
`55
`
`8
`In the cooling step, the acyl derivative is preferably
`crystallized into particles having an average particle
`size of about 10 microns or less.
`
`INDUSTRIAL APPLICABILITY
`
`The present compositions are used in a conventional
`manner for cleaning hair. From about 0.1 g to about 10
`g of a composition is applied to hair that has been wet-
`ted, generally with water, worked through the hair and
`then rinsed out.
`The following Examples further describe and demon-
`strate the preferred embodiments within the scope of
`the present invention. The Examples are given solely
`for the purpose of illustration and are not to be con-
`strued as limitations of the present invention as many
`variations thereof are possible without departing from
`its spirit and scope.
`EXAMPLES I—V
`
`The following compositions are representative of the
`present invention.
`
`II
`I
`18.00 18.00
`
`Weight %
`III
`18.00
`
`IV
`18.00
`
`V
`18.00
`
`4.00
`
`2.00
`
`2.00
`
`2.00
`
`2.00
`
`Component
`Cocamidopropyl
`Betaine
`Di-partially
`hydrogenated tallow
`dimethyl ammonium chloride
`Cetyltrimethylammonium
`chloride
`DC-200 Fluid (350 csk)1
`DC-200 Fluid (12500 csk)2
`DC-12483
`DC-X28107
`Citric Acid
`Ethylene Glycol
`Distearate
`4.50
`4.50
`PEG-3 Alkyl amide‘
`——
`1.00
`Sodium Chloride
`qs l00.000%
`Preservative, Dye,
`—
`—
`—
`-—
`—
`Perfume and Water
`
`pH 3.0 3.0 3.0 3.0 3.0
`
`
`
`
`‘Dimethylpolysiloxane offered by Dow Chemical Co.
`2Dimethylpo1ysi1oxane offered by Dow Chemical Co.
`3A dimethicone copolyol offered by Dow Chemical Co.
`‘PEG-3 Alkyl (98% C12) Amide - Mazarnide C-2 Experimental
`
`2.00
`
`—
`—
`1.oo
`—
`3.50
`1.50
`
`2.00
`
`1.75
`—
`—
`—
`3.50
`1.50
`
`2.00
`
`2.00
`
`— 1.00
`1.00 —
`—
`—
`—-
`—-—
`3.50
`3.50
`1.50
`1.50
`
`3.00
`—
`
`4.50
`—
`
`2.00
`
`—
`—
`-
`1.00
`3.50
`1.50
`
`4.50
`-
`
`These compositions are stable and deliver good con-
`ditioning to hair that is washed with the compositions.
`EXAMPLES VI & VII
`
`The following are two anionic shampoo composi-
`tions of the present invention.
`
`
`Component
`TEA C12—C14 Alkyl Sulfate
`NH4 C1z—C14 Alkyl (Ethoxy)3 Sulfate
`Sodium C12—C14 Alkyl Sulfate
`Cocamide MEA
`Dimethicone 1302001
`Ethylene Glycol Distearate
`Citric Acid
`Trisodium Citrate
`Q.S. Color, Preservative,
`Perfume and Water
`
`Weight %
`
`VI
`15.00
`—
`-—
`3.00
`3.00
`1.50
`0.60
`0.30
`g.s. 100%
`
`VII
`—
`7.90
`7.90
`1.50
`3.00
`1.50
`0.60
`-
`53.5. 100%
`
`65
`
`‘Po1ydimethylsiloxane having a viscosity of 12,500 centistokes
`
`These compositions are also stable and deliver good
`hair conditioning.
`
`The shampoos of the present invention can be made
`by mixing the materials together and heating to about
`72° C. The mixture is mixed thoroughly for about 10
`minutes at the 72° C. temperature before being pumped
`through a high shear mill and then through a heat ex-
`changer to cool it to about 27° C.
`The high shear mill is used to achieve adequate dis-
`persion of the silicone fluid. This is achieved by having
`the average particle size of the silicones preferably to
`about 10 microns or less.
`
`000005
`
`000005
`
`
`
`9
`
`EXAMPLE VIII
`
`4,741,855
`
`10
`2. A shampoo composition according to claim 1
`wherein the non-volatile silicone is selected from the
`group consisting of polydimethylsiloxanes having vis-
`cosities of from about 5 to about 100,000 centistokes at
`25° C., polypropylene oxide modified dimethylsiloxanes
`and silicone gums.
`_
`3. A shampoo composition according to claim 2
`wherein the surfactant is selected from the group con-
`sisting of amphoteric surfactants, zwitterionic surfac-
`tants and mixtures thereof.
`
`4. A shampoo composition according to claim 2
`wherein the surfactant is anionic.
`5. A shampoo composition according to claim 3
`wherein the non-volatile silicone is selected from the
`group consisting of polydimethylsiloxanes having vis-
`cosities of from about 5 to about 100,000 centistokes at
`25° C. and polypropylene oxide modified dimethylsilox-
`anes.
`
`6. A shampoo composition according to claim 5
`which in addition contains from about 0.01% to about
`10% of a quaternary ammonium compound.
`7. A shampoo composition according to claim 6
`wherein the surfactant is a betaine.
`8. A shampoo composition according to claim 7
`wherein the acyl derivative is ethylene glycol distea-
`rate.
`
`9. A shampoo composition according to claim 8
`wherein the shampoo composition has a pH of from
`about 2 to about 4.
`*
`it
`II!
`It
`*
`
`To demonstrate the benefit given by the ethylene
`glycol distearate to the present compositions, the com-
`positions of Examples I—V are prepared without the
`material. When samples were stored at 50° F., 80° F.
`and 100° F., all of the compositions without EGDS
`demonstrated instability with the silicone rising to the
`top in a clear layer. None of the compositions of the
`present
`invention demonstrated any instability. This
`clearly demonstrates the superiority of the present in-
`vention.
`What is claimed is:
`
`1. A shampoo composition comprising
`(a) from about 5% to about 70% of a synthetic surfac-
`tant selected from the group consisting of anionic
`surfactants, zwitterionic surfactants, amphoteric
`surfactants and mixtures thereof;
`(b) from about 0.01% to about 10% of a dispersed,
`insoluble, nonvolatile silicone;
`(c) from about 0.5% to about 5% of a long chain
`(C15—C22) acyl derivative or long chain (C15—C22)
`amine oxide selected from the group consisting of
`ethylene glycol long chain esters, alkanol amides of
`long chain fatty acids, long chain esters of long
`chain fatty acids, glyceryl long chain esters, long
`chain esters of long chain alkanolamides,
`long
`chain alkyl dimethyl amine oxides and mixtures
`thereof; and
`(d) the remainder water.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`45
`
`50
`
`55
`
`65
`
`000006
`
`000006