PCT
`WORLD rNTELLECfUAL PROPERTY ORGANIZATION
`International Bureau
`INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`wo 96/32919
`
`(51) International Patent Classification 6 :
`A61K 7/06
`
`Al
`
`(11) International Publication Number:
`
`(43) International Publication Date:
`
`24 October 1996 (24.10.96)
`
`(21) International Application Number:
`
`PCf/US96/04185
`
`(22) International Filing Date:
`
`27 March 1996 (27.03.96)
`
`(81) Designated States: AU, BR, CA, CN, JP, KR, MX, European
`patent (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT,
`LU, MC, NL, PT, SE).
`
`Published
`With international search report.
`Before the expiration of the time limit for amending the
`claims and to be republished in the event of the receipt of
`amendments.
`
`(30) Priority Data:
`08/428,923
`
`21 April 1995 (21.04.95)
`
`us
`
`THE PROCfER & GAMBLE COMPANY
`(71) Applicant:
`[US/US]; One Procter & Gamble Plaza, Cincinnati, OH
`45202 (US).
`
`(72) Inventors: COTHRAN, Philip, Earl; 3512 Shadowridge Drive,
`Loveland, OH 45140 (US). GAUTHIER, Thomas, Francis;
`1215 Emily Drive, Milford, OH 45150 (US). COFFINDAF(cid:173)
`FER, Timothy, Woodrow; 118 Bridle Lane, Loveland, OH
`45140 (US).
`
`(74) Agents: REED, T., David et at.; The Procter & Gamble
`Company, 5299 Spring Grove Avenue, Cincinnati, OH
`45217 (US).
`
`(54) Title: SHAMPOOS WITH INSOLUBLE SILICONE CONDITIONING AGENT AND CATIONIC POLYMER
`
`(57) Abstract
`
`Provided is an anti-dandruff shampoo composition comprising: (a) from about 8 % to about 40 %, by weight, of detersive surfactant,
`said composition comprising from about 5 % to about 40 %of anionic detersive surfactant; (b) from about 0.05 %to about 5 %, by weight,
`of a dispersed, insoluble silicone conditioning agent; (c) from about 0.01 % to about 1.0 %, by weight, of a stabilizing agent for the silicone
`conditioning agent, said stabilizing agent being a shampoo soluble cationic polymer; (d) from about 50% to about 91.5 %, by weight, water;
`wherein said shampoo composition is substantially free of suspending agents selected from the group consisting of crystalline suspending
`agents and anionic, nonionic, and amphoteric polymeric thickening agents.
`
`1
`
`

`
`FOR THE PURPOSES OF INFORMATION ONLY
`
`Codes used to identify States party to the Per on the front pages of pamphlets publishing international
`applications under the Per.
`
`AM
`AT
`AU
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`BY
`CA
`CF
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`CH
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`us
`uz
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`
`Malawi
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`Netherlands
`Norway
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`Slovakia
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`Swaziland
`Chad
`Togo
`Tajikistan
`Trinidad and Tobago
`Ukraine
`Uganda
`United States of America
`Uzbekistan
`VietNam
`
`2
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`W096/32919
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`PCf/US96/04185
`
`SHAMPOOS WITH INSOLUBLE SILICONE CONDITIONING AGENT AND
`CATIONIC POLYMER
`
`Technical Field
`The present invention relates to shampoo compositions containing
`an insoluble silicone conditioning agent. In particular, the present invention
`relates
`to shampoo compositions containing an
`insoluble silicone
`conditioning agent stably suspended with a low level of cationic polymer.
`Background of the Invention
`Shampoo compositions which both cleanse the hair and condition the
`hair with insoluble silicone conditioning agents are well known. Among the
`preferred types of insoluble silicone conditioning agents are nonvolatile
`polydimethyl siloxanes, which are typically dispersed in the shampoo as an
`emulsion, wherein the silicone is present as a dispersed phase of droplets
`in the aqueous shampoo formula.
`In order for these types of shampoos to
`be effective and to provide a consistent level of performance, without
`requiring vigorous shaking of the package in which they are contained, it is
`conventional practice to suspend them in the composition with the aid of a
`suspending agent. Since shampoos are likely to remain on shelves or in
`storage for long periods of time, it is important for the suspending agents to
`keep the insoluble conditioning agent well suspended for relatively long
`periods of time. The suspending agents which have become preferred for
`suspension of insoluble silicone conditioning agents are those which form a
`crystalline network in the shampoo when the shampoo is stationary, but
`which allow the composition to readily flow when shear is applied, such as
`when a user pours it out of a bottle. Examples of such crystalline
`suspending agents include ethylene glycol distearate and N, N- di-
`(hydrogenated tallow) amide benzoic acid.
`Another drawback of crystalline suspending agent is that they require
`costly heating and cooling steps in the manufacture of the compositions in
`order to make high quality stable suspensions.
`Yet another important parameter in the formulation of shampoos is
`lathering. The consuming p~blfc often associates high lathering with
`effective cleaning, and typically prefers high lathering shampoos to low
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`lathering shampoos from an aesthetic standpoint. Unfortunately, crystalline
`suspending agents tend to adversely affect lathering performance.
`Other suspending agents which are known
`include hydrophilic
`polymeric thickening agents such as cellulosic gums and crosslinked acrylic
`acid/acrylate polymers, the latter of which are commonly referred to as
`carbomers. Although these materials can be effective for suspending
`insoluble silicone they can impart an undesirable, slimy feel.
`It is well known in the art to add foaming agents to help compensate
`for lather reductions caused by suspending agents. Examples of such
`foaming agents
`include cocomono-and di-ethanol amide, betaine
`surfactants soluble longer chain alcohols such as C 12-C 14 monohydric
`alcohols, amine oxides, and cationic polymers such as cationic modified
`xanthan gum and hydroxy-ethyl cellulose. However, the addition of these
`ingredients does not overcome the other disadvantages of conventional
`suspending agents, adds further cost to the shampoo, and in certain cases
`may also increase harshness of the shampoo.
`It would be desirable to provide liquid shampoo composition with a
`stable dispersed insoluble silicone conditioning agent, which also did not
`require the use of conventional suspending agents such as crystalline
`suspending agents or polymeric thickening agents to suspend the silicone.
`It is therefore an object of this invention to provide shampoos
`containing insoluble silicone conditioning agents that are suspended without
`the need for crystalline suspending agents.
`It is yet another object of this invention to provide shampoos
`containing insoluble silicone conditioning agents that are suspended without
`the need for conventional, hydrophilic polymeric thickening agents.
`It is still another object of this invention to provide compositions, as
`set forth above, which can be made without the need for costly heating and
`cooling steps, as conventionally utilized when crystalline suspending agents
`are employed.
`It is yet another object of this invention to provide a process for
`making conditioning shampoos meeting the above objects. These and other
`benefits as may be apparent or otherwise realized can be obtained
`according to the present invention, which is described below. Unless
`otherwise indicated, all percentages are calculated by weight of the total
`composition, and all ratios are calculated on a weight basis. Unless
`otherwise indicated, ingredients are based on the active level and therefore
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`do not include carriers or by-products that may be included in commercially
`available materials. The present invention may comprise, consist of, or
`consist essentially of any of the essential and various optional and/or
`preferred ingredients and elements described herein. The terms "soluble"
`and "insoluble" shall refer to the solubility characteristics of a particular
`ingredient in the shampoo composition, unless otherwise specifically
`indicated. All viscosities and solubilities are determined at 2s•c, unless
`otherwise specifically indicated.
`SUMMARY OF THE INVENTION
`It has now been found that conditioning shampoos meeting the above
`In particular, it has been found that insoluble
`objects can be achieved.
`silicone conditioning agents in the form of dispersed droplets can be
`suspended in shampoo compositions containing anionic surfactants and
`relatively low levels of a shampoo-soluble cationic polymer, without the
`need for crystalline suspending agents or polymeric thickening agents for
`suspending the particles. By way of theory, and without intending to
`necessarily limit the invention, it is believed that the cationic polymers
`hereof form a net-like suspension by bridging miscelles of the anionic
`surfactant. The droplets of insoluble silicone become suspended within this
`network.
`It has been found that low levels of cationinc polymer can be
`highly effective for providing stability.
`More specifically, the present invention provides a conditioning
`shampoo composition comprising:
`to about 40%, by weight, of detersive
`(a)
`from about 8%
`surfactant, said composition containing at least about 5%, by
`weight, of anionic detersive surfactants;
`from about 0.05% to about 5%, by weight, of dispersed
`droplets of insoluble silicone;
`from about 0.01% to about 1.0%, by weight, of a stabilizing
`agent for said insoluble silicone, said stabilizing agent being a
`soluble cationic polymer;
`from about 50% to about 94.5%, by weight, water;
`(d)
`wherein said shampoo composition is substantially free of suspending
`agents selected from the group consisting of crystalline suspending agents
`and anionic, nonionic, and amphoteric polymeric thickening agents.
`invention can provide shampoos with excellent
`The present
`conditioning efficacy, cleansing, and lathering.
`In addition, the present
`
`(b)
`
`{c)
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`invention can result in significant cost savings in view of the elimination of
`conventional suspending agents such as crystalline suspending agents,
`which typically require separate heating and cooling steps to process the
`suspending agent. The present invention can also provide conditioning
`shampoo compositions which exhibit excellent deposition of silicone
`conditioning agents during use.
`Detailed Description of the Invention
`Detersive Surfactant Component
`The compositions of the present invention contain from about 8% to
`about 40% by weight, of detersive surfactant, preferably from about 1 0% to
`about 30%, more preferably from about 12% to about 25%. Included among
`the detersive surfactant hereof as a required element is an anionic detersive
`surfactant component. The compositions hereof can additionally contain
`nonionic and amphoteric surfactants, and mixtures thereof.
`The anionic detersive surfactant component will generally be present
`at a level of from about 5%, by weight of the composition, preferably at least
`about 8%, more preferably at least about 12%.
`Sulfate Surfactants
`The compositions hereof will preferably comprise alkyl sulfate, alkyl
`ethoxylated sulfate, or a mixture thereof.
`These materials have the
`respective formulae (I) ROS03M and (II) RO(C2H40)xS03M, wherein R is
`alkyl or alkenyl of from about 8 to about 30 carbon atoms, x is 1 to 10, and
`M is H or a salt-forming cation such as ammonium, alkanolamine containing
`triethanolamine, and monovalent and
`C1-C3 alkyl groups such as
`polyvalent metals such as the alkaline and alkaline earth metals. Preferred
`metals include sodium, potassium, magnesium, and calcium. The cation M,
`of the anionic surfactant should preferably be chosen such that the anionic
`surfactant component is water soluble. Solubility of anionic surfactants, in
`general, will depend upon the particular anionic surfactants and cations
`chosen.
`As an aid to determining appropriate mixtures of anionic
`surfactants, the anionic surfactants should be chosen such that the Krafft
`temperature is about 15°C or less, preferably about 1 ooc or less, more
`preferably about ooc or less. It is also preferred that the anionic surfactant
`be soluble in the composition hereof.
`Preferably, R has from about 1 0 to about 18 carbon atoms in both the
`alkyl and alkyl ethoxylated sulfates. The alkyl ethoxylated sulfates are
`typically made as condensation products of ethylene oxide and monohydric
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`alcohols having from about 8 to about 24 carbon atoms. The alcohols can
`be derived from fats, e.g., coconut oil, palm kernel oil, or tallow, or can be
`synthetic. Such alcohols are preferably reacted with about 1 to about 10,
`more preferably from about 1 to about 4, most preferably from about 2 to
`about 3.5, molar proportions of ethylene oxide and the resulting mixture of
`molecular species having, for example, an average of 3 moles of ethylene
`oxide per mole of alcohol, is sulfated and neutralized.
`Specific examples of alkyl ether sulfates which may be used in the
`present invention are sodium and ammonium salts of coconut alkyl
`triethylene glycol ether sulfate; tallow alkyl triethylene glycol ether sulfate,
`and tallow alkyl hexaoxyethylene sulfate. Highly preferred alkyl ether
`sulfates are those comprising a mixture of individual compounds, said
`mixture having an average alkyl chain length of from about 12 to about 16
`carbon atoms and an average degree of ethoxylation of from about 1 to
`about 4 moles of ethylene oxide.
`The sulfate surfactant is preferably comprised of a combination of
`ethoxylated and nonethoxylated sulfates. The weight ratio of alkyl sulfate to
`alkyl ethoxylated sulfate is preferably from about 4:1 to about 1:10, more
`preferably from about 2:1 to about 1:8, even more preferably from about 1:1
`to about 1:5, most preferably from about 1 :2 to about 1 :4. Weight ratios as
`described above are preferred
`for
`their ability
`to provide optimum
`combinations of lather, cleaning, and particulate anti-dandruff agent
`performance. Alkyl sulfates can provide excellent cleaning and lather
`performance. Alkyl ethoxylated sulfates can provide excellent cleaning
`performance, are mild to the skin, and can enhance deposition of the
`particulate anti-dandruff agent relative to alkyl sulfates.
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`Other Anionic Surfactants
`for use
`A preferred
`type of anionic surfactant, especially
`in
`combination with anionic sulfate surfactants, are the N-acyl amino acid
`surfactants. N-acyl amino acid surfactants, for purposes hereof, include N-
`acyl hydrocarbyl acids and salts thereof, such as those represented by
`Formula Ill, as follows:
`
`5
`
`0
`II
`Rl - C -
`
`R2
`I
`N -
`
`(R3)n- COOM
`
`(III)
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`20
`
`25
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`10 wherein: R1 is a Ca-C24 alkyl or alkenyl radical, preferably C1o-C18; R2 is
`-H, C1-C4 alkyl, phenyl, or -CH2COOM, preferably C1-C4 alkyl, more
`preferably C1-C2 alkyl; R3 is -CR42_ or C1-C2 alkoxy, wherein each R4
`independently is -H or C1-Cs alkyl or alkylester, and n is from 1 to 4,
`preferably 1 or 2; and M is H or a cation as previously defined, preferably an
`alkali metal such as sodium or potassium.
`A wide variety of N-acyl acid surfactants and their synthesis are
`described in Anionic Surfactants, Part II, Surfactant Science Series, Vol. VII,
`edited by Warner M. Linfield, Marcel Dekker, Inc. (New York and Basel),
`1976; pp 581-617.
`Especially preferred are compounds of Formula Ill wherein R2 is
`methyl and R3 is -CH2-. and n is 1, which are known as the N-acyl
`sarcosinates, and acids
`thereof.
`Specific examples
`include
`lauroyl
`sarcosinate, myristoyl sarcosinate, cocoyl sarcosinate, and oleoyl
`sarcosinate, preferably in their sodium and potassium salt forms.
`For the purposes of the surfactants described herein, it should be
`understood that the terms "alkyl" or "alkenyl" include mixtures of radicals
`which may contain one or more intermediate linkages such as ether or
`polyether linkages or non-functional substituents such as hydroxyl or
`halogen radicals wherein the radical remains of hydrophobic character.
`Anionic detersive surfactants also include aliphatic sulfonates, such
`as the water-soluble salts of the organic, sulfuric acid reaction products of
`the general formula (IV):
`(IV)
`R1-S03-M
`wherein R1 is chosen from the group consisting of a straight or branched
`chain, saturated aliphatic hydrocarbon radical having from about 8 to about
`24, preferably about 12 to about 18, carbon atoms; and M is a cation, as
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`previously described. Examples are the salts of an organic sulfuric acid
`reaction product of a hydrocarbon of the methane series, including iso-,
`nee-, and n-paraffins, having about 8 to about 24 carbon atoms, preferably
`about 12 about 18 carbon atoms and a sulfonating agent, e.g., S03,
`5 H2S04, oleum, obtained according to known sulfonation methods, including
`bleaching and hydrolysis. Preferred are alkali metal and ammonium
`sulfonated C12-C18 paraffins (e.g. normal and secondary paraffins).
`Additional examples of anionic detersive surfactants are the reaction
`products of fatty acids esterified with isethionic acid and neutralized with
`sodium hydroxide where, for example, the fatty acids are derived from
`coconut oil; sodium or potassium salts of fatty acid am ides of methyl tauride
`in which the fatty acids, for example, are derived from coconut oil. Other
`synthetic anionic detersive surfactants of this variety are set forth in U.S.
`Patents 2,486,921, 2,486,922, and 2,396,278.
`Still other anionic detersive surfactants are in the class designated as
`succinates. This class includes such surface active agents as disodium N(cid:173)
`N-(1 ,2-dicarboxyethyi)-N(cid:173)
`octadecylsulfosuccinate;
`tetrasodium
`octadecylsulfosuccinate; diamyl ester of sodium sulfosuccinic acid; dihexyl
`ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic
`acid.
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`Other suitable anionic detersive surfactants also include olefin
`sultanates having about 12 to about 24 carbon atoms. The term "olefin
`sultanates" is used herein to mean compounds which can be produced by
`the sulfonation of alpha-olefins by means of uncomplexed sulfur trioxide,
`followed by neutralization. of the acid reaction mixture in conditions such
`that any sulfones which have been formed in the reaction are hydrolyzed to
`give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide can
`be liquid or gaseous, and is usually, but not necessarily, diluted by inert
`dilutents, for example, by liquid S02, chlorinated hydrocarbons, etc., when
`used in the liquid form, or by air, nitrogen, gaseous S02, etc., when used in
`the gaseous form.
`The alpha-olefins from which the olefin sultanates are derived are
`mono-olefins having about 12 to about 24 carbon atoms, preferably about
`14 to about 16 carbon atoms. Preferably, they are straight chain olefins.
`In addition to the true alkene sultanates and a proportion of hydroxy-
`alkanesulfonates, the olefin sultanates can contain minor amounts of other
`materials, such as alkene disulfonates depending upon the reaction
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`conditions, proportion of reactants, the nature of the starting olefins and
`impurities in the olefin stock and side reactions during the sulfonation
`process.
`A specific alpha-olefin sulfonate mixture of the above type is
`described more fully in the U.S. Patent 3,332,880, Pflaumer and Kessler,
`issued July 25, 1967, incorporated herein by reference.
`Another class of anionic detersive surfactants are the beta-alkyloxy
`alkane sultanates. These compounds have the following formula (V):
`
`OR2 H
`I
`I
`R l -C - C -SOJM
`I
`I
`H
`H
`
`(V)
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`where R1 is a straight chain alkyl group having from about 6 to about 20
`carbon atoms, R2 is a lower alkyl group having from about 1 (preferred) to
`about 3 carbon atoms, and M is a cation as hereinbefore described.
`Many additional synthetic anionic surfactants are described in
`McCutcheon's Emulsifiers and Detergents, 1989 Annual, published by M. C.
`Publishing Co., which is incorporated herein by reference. Also U.S. Patent
`3,929,678, Laughlin et al., issued December 30, 1975, discloses many other
`anionic as well as other surfactant types and is incorporated herein by
`reference.
`Preferred anionic detersive surfactants for use in the present
`shampoo compositions include ammonium lauryl sulfate, ammonium laureth
`sulfate,
`triethylamine
`lauryl sulfate,
`triethylamine
`laureth sulfate,
`triethanolamine
`Iaury I
`sulfate,
`triethanolamine
`laureth
`sulfate,
`25 monoethanolamine
`lauryl sulfate, monoethanolamine
`laureth sulfate,
`diethanolamine
`lauryl sulfate, diethanolamine
`laureth sulfate,
`lauric
`monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate,
`potassium
`lauryl sulfate, potassium
`laureth sulfate, sodium
`lauryl
`sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine,
`ammonium cocoyl sulfate, ammonium lauroyl sulfate, sodium cocyl sulfate,
`sodium lauroyl sulfate, potassium cocoyl sulfate, potassium lauryl sulfate,
`triethanolamine
`lauryl
`sulfate,
`triethanolamine
`lauryl
`sulfate,
`monoethanolamine cocoyl sulfate, monoethanolamine lauryl sulfate, sodium
`tridecyl benzene sulfonate, and sodium dodecyl benzene sulfonate.
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`Amphoteric Surfactants
`Amphoteric surfactants can optionally be used
`the present
`in
`compositions and processes. Examples of amphoteric surfactants which
`can be used in the present invention include those which are broadly
`described as derivatives of aliphatic secondary and tertiary amines in which
`the aliphatic radical can be straight or branched chain 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,
`sulfonate, sulfate, phosphate, or phosphonate.
`the
`include
`The amphoteric surfactant hereof
`amphoteric surfactants such as those depicted by Formula VI:
`
`imidazolinium
`
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`13
`
`RlCON(CH2)nN+-CH2Z
`
`(VI)
`
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`15 wherein R1 is C8-C22 alkyl or alkenyl, preferably C12-C1s. R2 is hydrogen
`or CH2C02M, R3 is CH2CH20H or CH2CH20CH2CH COOM, R4 is
`hydrogen, CH2CH20H, or CH2CH20CH2CH2COOM, Z is C02M or
`CH2C02M, n is 2 or 3, preferably 2, M is hydrogen or a cation as described
`above.
`Suitable materials of this type are marketed under the tradename
`MIRANOL and are understood to comprise a complex mixture of species,
`and can exist in protonated and non-protonated species depending upon pH
`with respect to species that can have a hydrogen at R2. The imidazolinum
`imidazolinium
`amphoteric surfactant hereof can be derived via an
`intermediate. However, it will be recognized by those skilled in the art that it
`needn't necessarily be derived via an imidazolinium.
`Formula
`Preferred
`amphoteric
`surfactants
`of
`are
`VII
`monocarboxylates and dicarboxylates. Examples of these materials include
`cocoamphocarboxypropionic
`acid,
`cocoamphocarboxypropionate,
`cocoamphocarboxyglycinate
`(alternately
`referred
`to
`as
`cocoamphodiacetate ), and cocoamphoacetate.
`Specific commercial products providing the inidazolinium derivative
`component of the present compositions include those sold under the trade
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`-10-
`
`names MIRANOL C2M CONC. N.P., MIRANOL C2M CONC. O.P.,
`MIRANOL C2M SF, MIRANOL CM SPECIAL, MIRANOL ULTRA (Miranol,
`Inc.); ALKATERIC 2CIP (Aikaril Chemicals); AMPHOTERGE W-2 (Lonza,
`Inc.); MONATERIC CDX-38, MONATERIC CSH-32 (Mona
`Industries);
`5 REWOTERIC AM-2C (Rewo Chemical Group); and SCHEROTERIC MS-2
`(Scher Chemicals).
`Amphoteric surfactants also include aminoalkanoates of the formula
`
`(VII):
`
`10
`
`15
`
`20
`
`25
`
`R-NH(CH2)nCOOM;
`
`(VII) and
`
`iminodialkanoates of the formula (VIII):
`
`R-N[(CH2)mCOOM]2
`
`(VIII)
`
`and mixtures thereof; wherein n and m are numbers from 1 to 4, R is Ca(cid:173)
`C22 alkyl or alkenyl, and M is hydrogen or a cation as described above.
`n-
`Examples
`of
`such
`amphoteric
`surfactants
`include
`alkylaminopropionates and n-alkyliminodipropionates. Such materials are
`sold under the tradename DERIPHAT by Henkel and MIRATAINE by
`Miranol, Inc. Specific examples include N-lauryl-beta-amino propionic acid
`or salts thereof, and N-lauryl-beta-imino-dipropionic acid or salts thereof.
`Other amphoteric surfactants that can be used include betaine
`surfactants such as to be excluded include those represented by the
`Formula (IX):
`
`~ I
`
`C -N-(CH2)m
`
`Rs
`
`(IX)
`
`n
`
`12
`
`

`
`wo 96/32919
`
`PCI'IUS96/04185
`
`-11-
`
`5
`
`wherein:
`R1 is a member selected from the group consisting of
`COOM and CH-CH2S03M
`I
`OH
`R2 is C1-C3 alkyl or hydroxy (C1-C3) alkyl;
`R3 is C1-C3 alkyl or hydroxy (C1-C3) alkyl;
`R4 is a member selected from the group consisting of hydrogen and C1-
`C3 alkyl;
`10 Rs is C8-C2o alkyl or alkenyl;
`Y is C1-C3 alkyl;
`m is an integer from 2 to 7;
`n is the integer 1 or 0;
`M rs hydrogen or a cation as described above.
`15 Nonionic Surtactants
`Nonionic detersive surfactants can also optionally be used in the
`present invention. Nonionic surfactants include those 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 detersive surfactants are:
`1. The polyethylene oxide condensates of alkyl phenols, e.g., the
`condensation products of alkyl phenols having an alkyl group containing
`from about 6 to about 20 carbon atoms in either a straight chain or
`branched chain configuration, with ethylene oxide, the said ethylene oxide
`being present in amounts equal to from about 1 0 to about 60 moles of
`ethylene oxide per mole of alkyl phenol.
`2. Those derived from the condensation of ethylene oxide with the
`product resulting from the reaction of propylene oxide and ethylene diamine
`products.
`3. The condensation product of aliphatic alcohols having from about
`8 to about 18 carbon atoms, in either straight chain or branched chain
`configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide
`condensate having from about 1 0 to about 30 moles of ethylene oxide per
`35 mole of coconut alcohol, the coconut alcohol fraction having from about 10
`to about 14 carbon atoms.
`4. Long chain tertiary amine oxides corresponding to the following
`general formula:
`
`20
`
`25
`
`30
`
`13
`
`

`
`_____ - - - - - - -
`
`W096/32919
`
`PCT/US96/04185
`
`-12-
`
`R1R2R3N ~ 0
`wherein R1 contains an alkyl, alkenyl or monohydroxy alkyl radical of from
`about 8 to about 18 carbon atoms, from 0 to about 1 0 ethylene oxide
`moieties, and from 0 to about 1 glyceryl moiety, and R2 and R3 contain from
`about 1 to about 3 carbon atoms and from 0 to about 1 hydroxy group, e.g.,
`the arrow in
`methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals.
`the formula is a conventional representation of a semipolar bond.
`5.
`Long chain tertiary phosphine oxides corresponding to the
`following general formula:
`RR'R"P ~o
`wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging
`from about 8 to about 18 carbon atoms in chain length, from 0 to about 1 0
`ethylene oxide moieties and from 0 to about 1 glyceryl moiety and R' and R"
`are each alkyl or monohydroxyalkyl groups containing from about 1 to about
`3 carbon atoms.
`6. Long chain dialkyl sulfoxides containing one short chain alkyl or
`hydroxy alkyl radical of from about 1 to about 3 carbon atoms (usually
`methyl) and one long hydrophobic chain which include alkyl, alkenyl,
`hydroxy alkyl, or keto alkyl radicals containing from about 8 to about 20
`carbon atoms, from 0 to about 1 0 ethylene oxide moieties and from 0 to
`about 1 glyceryl moiety.
`7.
`Alkyl polysaccharide (APS) surfactants such as the alkyl
`polyglycosides. Such surfactants are described in U.S. Patent 4,565,647,
`Llenado, issued January 21, 1986, incorporated herein by reference, which
`discloses APS surfactants having a hydrophobic group with about 6 to
`about 30 carbon atoms and polysaccharide (e.g., polyglycoside) as the
`hydrophilic group. Optionally, there can be a polyalkylene-oxide group
`joining the hydrophobic and hydrophilic moieties. The alkyl group (i.e., the
`hydrophobic moiety) can be saturated or unsaturated, branched or
`unbranched, and unsubstituted or substituted (e.g., with hydroxy or cyclic
`rings).
`
`8. Polyethylene glycol (PEG) glyceryl fatty esters, such as those of
`the formula R(O)OCH2CH(OH)CH2(0CH2CH2)nOH wherein n is from
`about 5 to about 200, preferably from about 20 to about 100, and R is an
`aliphatic hydrocarbyl having from about 8 to about 20 carbon atoms.
`9. Polyhydroxy fatty acid ami des of the formula:
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`14
`
`

`
`W096/32919
`
`PCI'/US96/0418S
`
`-13-
`
`0 Rl
`II
`I
`R2-C-N-Z
`
`10
`
`15
`
`wherein: R1 is H,2C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or
`a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl,
`most preferably C1 alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl
`5 moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably
`straight chain C9-C 17 alkyl or alkenyl, most preferably straight chain C11-
`C15 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl
`moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly
`connected to the chain, or an alkoxylated derivative (preferably ethoxylated
`or propoxylated) thereof. Z preferably will be derived from a reducing sugar
`in a reductive amination reaction; more preferably Z is a glycityl moiety.
`Suitable reducing sugars include glucose, fructose, maltose,
`lactose,
`galactose, mannose, and xylose. As raw materials, high dextrose com
`syrup, high fructose corn syrup, and high maltose corn syrup can be utilized
`as well as the individual sugars listed above. These corn syrups may yield
`It should be understood that it is by no
`a mix of sugar components for Z.
`means intended to exclude other suitable raw materials. Z preferably will be
`selected
`from
`the group consisting of
`-CH2-(CHOH)n-CH20H,
`-
`CH(CH20H)-(CHOH)n-1-CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH20H,
`20 where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or
`aliphatic monosaccharide, and alkoxylated derivatives thereof. Most
`preferred are glycityls wherein n is 4, particularly -CH2-{CHOH)4-CH20H.
`In the above formula, R1 can be, for example, N-methyl, N-ethyl, N(cid:173)
`propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
`R2-CO-N< can be, for example, cocamide, stearamide, oleamide,
`lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
`Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-
`deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
`Polyhydroxy fatty acid amides are disclosed, for example, in G.B.
`30 Patent Specification 809,060, published February 18, 1959, by Thomas
`Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E.
`R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March
`8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott,
`each of which is incorporated herein by reference.
`When used, the optional amphoteric and nonionic surfactants are
`typically present at levels of from about 0.05% to about 20%, more typically
`
`25
`
`35
`
`15
`
`

`
`W096/Jl919
`
`PCTIUS96/04185
`
`-14-
`
`5
`
`15
`
`20
`
`from about 0.1% to about 10%, preferably from about 0.5% to about 5%,
`although higher or lower levels can be