United States Patent [19]
`Coffindaffer et al.
`
`II ~111111111111
`
`US005624666A
`[11] Patent Number:
`[451 Date of Patent:
`
`5,624,666
`Apr. 29, 1997
`
`[54] ANTI-DANDRUFF SHAMPOOS WITH
`PARTICULATE ACTIVE AGENT AND
`CATIONIC POLYMER
`
`[75]
`
`Inventors: Timothy W. Coffindaffer; Philip E.
`Cothran. both of Loveland; Thomas F.
`Gauthier. Milford. all of Ohio
`
`[73] Assignee: The Procter & Gamble Company.
`Cincinnati. Ohio
`
`[21] Appl. No.: 375,457
`Jan. 20, 1995
`
`[22] Filed:
`Int. Cl.6
`....................................................... A61K 7/06
`[51]
`[52] U.S. Cl . ..................................... 424n0.21; 424/70.22;
`424/70.24; 424/70.28; 514/880; 514/881
`[58] Field of Search .............................. 424/70.21, 70.22,
`424/70.24. 70.28; 514/880. 881
`
`[56]
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`4;273,7(/J
`4;298,494
`4,830,774
`4,835,148
`4,997,641
`
`611981 Koehler et al ....................... 424170.24
`1111981 Parslow et al .......................... 252/550
`5/1989 LaPetina et al ......................... 514/852
`5/1989 Barford et al .......................... 514/881
`3/1991 Hartnett et al ....................... 424170.28
`
`5,104,645
`5,145,ffJ7
`5,149,522
`5,393,519
`
`4/1992 Cardin et al ............................ 514/852
`9/1992 Rich ..................................... 424170.28
`9/1992 Schwarz et al ...................... 424170.28
`2/1995 Dowell et al ........................ 424170.24
`
`Primary Examiner-Mark D. Sweet
`Attorney, Agent, or Finn-Leonard W. Lewis; Anthony D.
`Sabatelli; David K. Dabbiere
`ABSTRACT
`
`[57]
`
`Provided is a anti-dandruff shampoo composition compris(cid:173)
`ing: (a) from about 8% to about 40%, by weight, of anionic
`detersive surfactant; (b) from about 0.1% to about 5%, by
`weight, of particulate anti-dandruff agent having an average
`particle size of from about 0.35 microns to about 5 microns;
`(c) from about 0.01% to about 1.0%. by weight. of a
`stabilizing agent for said anti-dandruff agent. said stabilizing
`agent being a soluble cationic polymer; (d)from about 50%
`to about 91.89%. 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
`suspending agents. Also provided is a process used for
`making the present compositions wherein said particulate
`anti -dandruff agent and said cationic polymer are admixed in
`water in the presence of anionic detersive surfactant.
`
`17 Claims, No Drawings
`
`1
`
`

`

`5,624,666
`
`1
`ANTI-DANDRUFF SHAMPOOS WITH
`PARTICULATE ACTIVE AGENT AND
`CATIONIC POLYMER
`
`TECHNICAL FIELD
`
`The present invention relates to shampoo compositions
`containing particulate anti-dandruff agents. In particular, the
`present invention relates to shampoo compositions contain(cid:173)
`ing a particulate anti-dandruff agent and a cationic polymer.
`
`BACKGROUND OF THE INVENTION
`
`5
`
`Shampoo compositions for cleaning the hair which also
`contain anti-dandruff agents are well known. Among the
`preferred types of anti-dandruff agents are particulate, crys(cid:173)
`talline anti-dandruff agents, such as sulfur, selenium
`disulfide, and heavy metal salts of pyridinethione. 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 20
`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
`particulate anti-dandruff agents well suspended for rela- 25
`tively long periods of time. The suspending agents which
`have become preferred for suspension of particulate anti(cid:173)
`dandruff 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, 30
`such as when a user pours it out of a bottle. Examples of
`such suspending agents include ethylene glycol distearate
`and N. N- di- (hydrogenated tallow) arnido benzoic acid.
`Crystalline suspending agents are currently the preferred
`method for suspending particulate anti-dandruff agents in 35
`the marketplace.
`Other suspending agents which are known include hydro(cid:173)
`philic polymeric thickening agents such as cellulosic gums
`and acrylic acid/acrylate polymers, the latter of which are
`commonly referred to as carbomers. Although these mate- 40
`rials are effective for suspending particulate matter, at higher
`levels they tend to impart an undesirable, slimy feel.
`Just as important as suspending the anti-dandruff agent ,
`the suspending agent must also allow the anti-dandruff agent
`to deposit on the scalp during use. If too little anti-dandruff 45
`agent deposits, it will be unable to provide good anti(cid:173)
`dandruff efficacy. The polymeric suspending agents are
`believed to be less efficient than the crystalline suspending
`agents for deposition of active ingredients on the scalp and
`hair.
`Another drawback of crystalline suspending agent is that
`they require costly heating and cooling steps in the manu(cid:173)
`facture of the compositions in order to make high quality
`stable suspensions.
`Another important parameter in the formulation of anti(cid:173)
`dandruff shampoos is lathering. The consuming public often
`associates high lathering with effective cleaning, and typi(cid:173)
`cally prefers high lathering shampoos to low lathering
`shampoos from an aesthetic standpoint. Unfortunately, crys- 60
`talline suspending agents tend to adversely affect lathering
`performance.
`It is also known to prepare antimicrobial compositions
`utilizing finely powdered polyvalent metal salts of
`2-mercaptopyridine-N-oxide, e.g., zinc pyridinethione. See, 65
`for example, U.S. Pat. No. 4,832,950 (Takaya et al .. issued
`May 23, 1989) and U.S. Pat. No. 4.670.430 (Inamura et al.,
`
`2
`issued Jun. 2, 1987). In these compositions, very small
`average particle size of less than 0.2 microns, are said to
`provide improved dispersion stability without the use of
`polymeric suspending agents or other means to suspend
`larger particles. Compared to such prior compositions, the
`compositions of Imamura et al. are said to provide improved
`adsorbability. Takaya et al. teaches further suspension sta(cid:173)
`bility of the small particles of Imamura et al. via the use of
`a specific dispersent selected from the group consisting of:
`10 (A) polyglycol/polyamine polyglycol/polyamine/
`alkylamine or alkylenearnine condensation polymers; (B)
`water soluble polymers selected from the group consisting
`of hydroxyalkylcelluloses and partly quaternized products
`thereof. and at least one nonionic surfactant; and (C) at least
`15 one cationic polymer compound and at least one inorganic
`salt.
`Although the above compositions avoid the use of con(cid:173)
`ventional suspending agents. deposition efficiency of the
`particulate metal salts remains impaired due to the extremely
`small size of these particles. Because of their small size, a
`proportion of them would tend to remain dispersed in
`solution rather than deposit on the scalp, skin, or hair.
`Thus, it would be desirable to provide liquid topical
`composition with a stable dispersed anti-dandruff agent.
`which utilized larger particles than those specified in the
`above patents, but which also did not require the use of
`conventional suspending agents such as crystalline suspend(cid:173)
`ing agents or polymers added for thickening purposes.
`It is an object of this invention to provide anti-dandruff
`shampoos containing particulate anti-dandruff agents that
`are suspended without the need for crystalline suspending
`agents. but which still retain efficient deposition of the
`anti-dandruff agent on the hair or scalp. It is another object
`of this invention to provide anti-dandruff shampoos contain(cid:173)
`ing particulate anti-dandruff agents that are suspended with(cid:173)
`out the need for hydrophilic polymeric thickening agents,
`but which still retain efficient deposition of the anti-dandruff
`agent on the hair or scalp.
`It is another object of this invention to provide such
`compositions, as set forth above, which have good, non(cid:173)
`slimy feel. It is yet another object of this invention to provide
`compositions as set forth above which have improved depo(cid:173)
`sition efficiency on the skin, scalp and/or hair, relative to
`conventional suspending agents for particulate matter in
`liquid topical compositions. 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 suspend(cid:173)
`ing agents are employed.
`It is yet another object of this invention to provide a
`process for making anti-dandruff shampoos meeting the
`above objects.
`
`50
`
`55
`
`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 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.
`
`2
`
`

`

`10
`
`Detersive Surfactant Component
`
`15
`
`45
`
`5,624,666
`
`4
`the case of crystalline suspending agents require separate
`heating and cooling steps to process the suspending mate(cid:173)
`rial. In addition, the compositions hereof can provide
`enhanced lathering and excellent deposition of anti-dandruff
`5 actives on the skin, scalp and/or hair.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`The compositions of the present invention contain an
`anionic detersive surfactant component, which preferably
`comprises alkyl sulfate, alkyl ethoxylated sulfate, or a
`mixture thereof. The compositions hereof can also comprise
`other types of anionic surfactants, and can additionally
`contain nonionic and amphoteric surfactants.
`The anionic detersive surfactant component will generally
`be present at a level from about 8% to about 40%. by weight
`of the composition, preferably from about 10% to about
`20 30%. more preferably from about 12% to about 22%.
`
`3
`SUMMARY OF THE INVENTION
`It has now been found that anti-dandruff shampoos meet(cid:173)
`ing the above objects can be achieved. In particular, it has
`been found that relatively small particle size particulate
`anti-dandruff agents can be suspended in shampoo compo(cid:173)
`sitions containing anionic surfactants and relatively low
`levels of a shampoo soluble cationic polymer, without the
`need for crystalline suspending agents or polymeric thick(cid:173)
`ening agents for suspending the particles. The present com-
`positions utilize particles having an average particle diam-
`eter of from about 0.35 microns to about 5 microns. 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 small particle size particulate anti-
`dandruff agent then becomes suspended within this network.
`More specifically, the present invention provides an anti(cid:173)
`dandruff shampoo composition comprising:
`(a) from about 8% to about 40%, by weight, of anionic
`detersive surfactant;
`Sulfate Surfactants
`(b) from about 0.1% to about 5%, by weight, of particu(cid:173)
`late anti-dandruff agent having an average particle size
`The compositions hereof will preferably comprise alkyl
`of from about 0.35 microns to about 5 microns;
`sulfate, alkyl ethoxylated sulfate, or a mixture thereof. These
`(c) from about 0.01% to about 1.0%, by weight, of a 25
`materials have the respective formulae (I) ROS03M and (II)
`stabilizing agent for said anti-dandruff agent, said sta(cid:173)
`RO(C2H40)))03M, wherein R is alkyl or alkenyl of from
`bilizing agent being a soluble cationic polymer;
`about 8 to about 30 carbon atoms. x is 1 to 10, and M is H
`(d) from about 50% to about 91.89%, by weight. water;
`or a soluble salt-forming cation such as ammonium,
`wherein said shampoo composition is substantially free of
`alkanolarnine, such triethanolamine, monovalent metals,
`suspending agents selected from the group consisting of 30
`such as sodium and potassium, and polyvalent metal cations,
`crystalline suspending agents and anionic, nonionic, and
`such as magnesium and calcium. The cation M, of the
`amphoteric polymeric suspending agents.
`anionic surfactant should be chosen such that the anionic
`It has also been found that the process used for making the
`surfactant component is water soluble. Solubility of anionic
`present compositions can be critical to stability of the final
`surfactants, in general, will depend upon the particular
`product. In particular, the particulate anti-dandruff agent and 35
`anionic surfactants and cations chosen. As an aid to deter(cid:173)
`cationic polymer should preferably be combined or admixed
`mining appropriate mixtures of anionic surfactants, the
`with one another only in aqueous conditions in the presence
`anionic surfactants should be chosen such that the Krafft
`of anionic surfactant. Combining the particulate anti(cid:173)
`temperature is about 15° C. or less, preferably about 10° C.
`dandruff agent and cationic polymer under aqueous
`or less, more preferably about 0° C. or less. It is also
`conditions. in the absence of anionic surfactant can undes- 40
`preferred that the anionic surfactant be soluble in the com(cid:173)
`ireably lead to agglomeration of the particulate anti-dandruff
`position hereof.
`agent.
`Preferably, R has from about 10 to about 18 carbon atoms
`More specifically, the present invention provides a pro(cid:173)
`in both the alkyl and alkyl ethoxylated sulfates. The alkyl
`cess for making a stable anti-dandruff shampoo composition
`ethoxylated sulfates are typically made as condensation
`comprising preparing a mixture of:
`products of ethylene oxide and monohydric alcohols having
`(a) from about 8% to about 40%. by weight, anionic
`from about 8 to about 24 carbon atoms. The alcohols can be
`detersive surfactant;
`derived from fats, e.g .. coconut oil, palm kernel oil, or
`(b) from about 0.1% to about 5%, by weight, of particu(cid:173)
`tallow, or can be synthetic. Such alcohols are preferably
`late anti-dandruff agent having a volume average par- 50
`reacted with about 1 to about 10, more preferably from about
`1 to about 4, most preferably from about 2 to about 3.5,
`tide size of from about 0.35 microns to about 5
`microns;
`molar proportions of ethylene oxide and the resulting mix(cid:173)
`ture of molecular species having, for example, an average of
`(c) from about 0.01% to about 1%, by weight, of stabi(cid:173)
`3 moles of ethylene oxide per mole of alcohol, is sulfated
`lizing agent for said anti-dandruff agent, said stabiliz(cid:173)
`ing agent being a shampoo soluble cationic polymer; 55 and neutralized.
`Specific examples of alkyl ether sulfates which may be
`(d) from about 50% to about 91.89%, by weight, water;
`used in the present invention are sodium and ammonium
`wherein said particulate anti-dandruff agent and said cat(cid:173)
`salts of coconut alkyl triethylene glycol ether sulfate; tallow
`ionic polymer are admixed in water in the presence of
`alkyl triethylene glycol ether sulfate, and tallow alkyl
`anionic detersive surfactant, and said composition is sub(cid:173)
`60 hexaoxyethylene sulfate. Highly preferred alkyl ether sul(cid:173)
`stantially free of crystalline suspending agents and anionic,
`fates are those comprising a mixture of individual
`amphoteric, and nonionic polymeric suspending agents.
`compounds, said mixture having an average alkyl chain
`The present invention can provide shampoos with excel(cid:173)
`length of from about 12 to about 16 carbon atoms and an
`lent anti-dandruff efficacy, cleansing, and lathering. In
`average degree of ethoxylation of from about 1 to about 4
`addition, the present invention can result in significant cost
`65 moles of ethylene oxide.
`savings in view of the elimination of conventional suspend(cid:173)
`ing agents, which are typically used at higher levels than are
`The sulfate surfactant is preferably comprised of a com(cid:173)
`the cationic polymers of the present invention, or which in
`bination of ethoxylated and nonethoxylated sulfates. The
`
`3
`
`

`

`5,624,666
`
`5
`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 5
`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 excel(cid:173)
`lent cleaning performance. are mild to the skin, and can 10
`enhance deposition of the particulate anti-dandruff agent
`relative to alkyl sulfates.
`
`Other Anionic Surfactants
`A preferred type of anionic surfactant, especially for use
`in combination with anionic sulfate surfactants. are the
`N-acyl amino acid surfactants. N-acyl amino acid
`surfactants, for pmposes hereof. include N-acyl hydrocarbyl
`acids and salts thereof. such as those represented by Formula
`III, as follows:
`
`6
`according to known sulfonation methods, including bleach(cid:173)
`ing and hydrolysis. Preferred are alkali metal and ammo(cid:173)
`nium sulfonated C12-C18 paraffins (e.g. normal and second-
`ary paraffins).
`Additional examples of anionic detersive surfactants
`which come within the terms of the present invention 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 amides 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. Pat. Nos. 2.486.921; 2.486,922;
`and 23%,278.
`Still other anionic detersive surfactants are in the class
`15 designated as succinates. This class includes such surface
`active agents as disodium N-octadecylsulfosuccinate; tetra(cid:173)
`sodium N-( 1,2-dicarboxyethyl)- N-octadecylsulfosuccinate;
`diamyl ester of sodium sulfosuccinic acid; dihexyl ester of
`sodium sulfosuccinic acid; dioctyl esters of sodium sulfos-
`20 uccinic acid.
`Other suitable anionic detersive surfactants include olefin
`.sulfonates having about 12 to about 24 carbon atoms. The
`term "olefin sulfonates" is used herein to mean compounds
`which can be produced by the sulfonation of alpha-olefins
`25 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(cid:173)
`alkanesulfonates. The sulfur trioxide can be liquid or
`30 gaseous, and is usually. but not necessarily, diluted by inert
`dilutents, for example. by liquid so2. 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 sulfonates are
`35 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 sulfonates and a proportion
`of hydroxy-alkanesulfonates. the olefin sulfonates can con-
`40 tain minor amounts of other materials, such as alkene
`disulfonates depending upon the reaction conditions. pro(cid:173)
`portion 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. Pat. No. 3332.880,
`Pfiaumer and Kessler, issued Jul. 25, 1967. incorporated
`herein by reference.
`Another class of anionic detersive surfactants are the
`50 betaalkyloxy alkane sulfonates. These compounds have the
`following formula (V):
`
`(III)
`
`0 R2
`II
`I
`R 1-C -N -(R3).-COOM
`wherein: R1 is a C8-C24 alkyl or alkenyl radical, preferably
`C10-C18; R2 is -H. C1-C4 alkyl. phenyl. or -CH2COOM,
`preferably C1-C4 alkyl. more preferably C1-C2 alkyl; R3 is
`-CR4
`2-or CcC2 alkoxy, wherein each R4 independently
`is -H or CcC6 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 potas(cid:173)
`sium.
`A wide variety of N-acyl acid surfactants and their
`synthesis are described in Anionic Suifactants, Part II,
`Suifactant Science Series, Vol. VII. edited by Warner M.
`llnfield, Marcel Dekker, Inc. (New York and Basel), 1976;
`pp 581-617.
`Especially preferred are compounds of Formula III
`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, pref(cid:173)
`erably 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" 45
`include mixtures of radicals which may contain one or more
`intermediate linkages such as ether or poly ether linkages or
`non-functional substituents such as hydroxyl or halogen
`radicals wherein the radical remains of hydrophobic char(cid:173)
`acter.
`Another type of anionic detersive surfactants are aliphatic
`sulfonates such as represented by the water-soluble salts of
`the organic, sulfuric acid reaction products of the general
`formula (N):
`
`ORz H
`I
`I
`Rl-C-C-SO)hl
`I
`I
`H
`H
`
`(V)
`
`55
`
`(IV)
`
`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 previously 60
`described. subject to the same limitations regarding polyva(cid:173)
`lent metal cations as previously discussed. Important
`examples are the salts of an organic sulfuric acid reaction
`product of a hydrocarbon of the methane series, including
`iso-, neo-. and n-paraffins, having about 8 to about 24 carbon 65
`atoms, preferably about 12 about 18 carbon atoms and a
`sulfonating agent, e.g .• S03 , H2S04 , oleum. obtained
`
`where R 1 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 water-soluble 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. Pat. No. 3.929,
`678. Laughlin et al., issued Dec. 30. 1975, discloses many
`other anionic as well as other surfactant types and is incor(cid:173)
`porated herein by reference.
`
`4
`
`

`

`5,624,666
`
`8
`38, MON.IITERIC CSH-32 (Mona Industries); REWOT(cid:173)
`ERIC AM-2C (Rewo Chemical Group); and SCHEROT(cid:173)
`ERIC MS-2 (Scher Chemicals).
`Amphoteric surfactants also include aminoalkanoates of
`the formula (Vll):
`
`R-NH(CH2)nCOOM;
`
`(VII) and
`
`iminodialkanoates of the formula (Vlll):
`
`(VDI)
`
`7
`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 lauryl
`sulfate. triethanolamine laureth sulfate, monoethanolamine 5
`lauryl sulfate, monoethanolamine laureth sulfate. diethano(cid:173)
`lamine 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 10
`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. tri(cid:173)
`ethanolamine lauryl sulfate, monoethanolamine cocoyl 15
`sulfate. monoethanolarnine lauryl sulfate, sodium tridecyl
`benzene sulfonate. and sodium dodecyl benzene sulfonate.
`
`Amphoteric Surfactants
`
`Amphoteric surfactants can optionally be used in the
`present compositions and processes. Examples of amphot(cid:173)
`eric 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 ali(cid:173)
`phatic 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 amphoteric surfactant hereof include the imidazo-
`linium amphoteric surfactants such as those depicted by
`Formula VI:
`
`and mixtures thereof; wherein n and m are numbers from 1
`to 4, R is C8-C22 alkyl or alkenyt and M is hydrogen, alkali
`metal, alkaline earth metal, ammonium or alkanolammo-
`nium.
`Examples of such amphoteric surfactants include
`n-alkylaminopropionates and n-alkylirninodipropionates.
`Such materials are sold under the tradename DERIPHAT by
`Henkel and MIRATAINE by Miranol. Inc. Specific
`20 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
`25 represented by the Formula (IX):
`
`I4
`0
`II
`I
`C-N-(CH2)m
`
`LR2
`I
`n r+-Y-RI
`
`--{
`Rs
`
`(IX)
`
`30
`
`RJ
`
`wherein:
`R 1 is a member selected from the group consisting of
`
`(VI) 35
`
`COOM and CH -CH2S03M
`I
`OH
`
`R2 is C 1-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;
`R5 is C8-C20 alkyl or alkenyl;
`Y is C1-C3 alkyl;
`m is an integer from 2 to 7;
`n is the integer 1 or 0;
`M is hydrogen or a cation. such as an alkali metal or
`alkaline earth cation metal, ammonium. or alkanola(cid:173)
`mide.
`The term "alkyl" or "hydroxyalkyl" means straight or
`branch chained, saturated, aliphatic hydrocarbon radicals
`and substituted hydrocarbon radicals such as. for example,
`methyl. ethyl, propyL isopropyl, hydroxypropyl,
`hydroxyethyl. and the like.
`
`Nonionic Surfactants
`
`45
`
`wherein R1 is C8-C22 alkyl or alkenyl, preferably C12-C16,
`R 2 is hydrogen or CH2C02M, R3 is CH2CH20H or 40
`CH2CH20CH2CH COOM, R4 is hydrogen, CH2CH20H. or
`CH2CH20CH2CH2COOM, Z is COzM or CH2C02M, n is
`2 or 3, preferably 2. M is hydrogen or a cation, such as alkali
`metal, alkaline earth metal, ammonium. or alkonol ammo(cid:173)
`nium.
`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 50
`amphoteric surfactant hereof can be derived via an imida(cid:173)
`zolinium intermediate. However, it will be recognized by
`those skilled in the art that it needn't necessarily be derived
`via an imidazolinium.
`Preferred amphoteric surfactants of Formula Vll are 55
`monocarboxylates and dicarboxylates. Examples of these
`materials include cocoamphocarboxypropionate, cocoam(cid:173)
`phocarboxypropionic acid, cocoamphocarboxyglycinate
`(alternately referred to as cocoamphodiacetate), and coco(cid:173)
`amphoacetate.
`Specific commercial products providing the inidazo(cid:173)
`linium derivative component of the present compositions.
`include those sold under the trade names MIRANOL C2M
`CONC. N.P., MIRANOL C2M CONC. O.P.. MIRANOL
`C2M SF. MIRANOL CM SPECIAL, MIRANOL ULTRA 65
`(Miranol, Inc.); ALKJITERIC 2CIP (Alkaril Chemicals);
`AMPHOTERGE W-2 (Lonza, Inc.); MON.IITERIC CDX-
`
`Nonionic detersive surfactants can also optionally be used
`in the present invention. Nonionic surfactants include those
`60 broadly defined as compounds produced by the condensa(cid:173)
`tion 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
`
`5
`
`

`

`5,624,666
`
`10
`aliphatic hydrocarbyl having from about 8 to about 20
`carbon atoms.
`9. Polyhydroxy fatty acid arnides of the formula:
`
`0 R1
`II
`I
`R2-C-N-Z
`
`5
`
`9
`carbon atoms in either a straight chain or branched
`chain configuration, with ethylene oxide, the said eth(cid:173)
`ylene oxide being present in amounts equal to from
`about 10 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 propy(cid:173)
`lene oxide and ethylene diamine products.
`3. The condensation product of aliphatic alcohols having
`from about 8 to about 18 carbon atoms, in either 10
`straight chain or branched chain configuration, with
`ethylene oxide, e.g., a coconut alcohol ethylene oxide
`condensate having from about 10 to about 30 moles of
`ethylene oxide per mole of coconut alcohol. the coco(cid:173)
`nut alcohol fraction having from about 10 to about 14 15
`carbon atoms.
`4. Long chain tertiary amine oxides corresponding to the
`following general formula:
`
`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 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 .. methyl. ethyl. propyl.
`hydroxyethyl. or hydroxypropyl radicals. the arrow in
`the formula is a conventional representation of a semi-
`polar bond.
`5. Long chain tertiary phosphine oxides corresponding to
`the following general formula:
`
`RR'R"P-40
`
`20
`
`25
`
`30
`
`35
`
`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 C5-C31
`hydrocarbyl moiety, preferably straight chain ~-C19
`alkyl or alkenyl. more preferably straight chain C9-C17
`alkyl or alkenyl. most preferably straight chain C11-C15
`alkyl or alkenyl. or mixture thereof; and Z is a poly-
`hydroxyhydrocarbyl moiety having a linear hydrocar(cid:173)
`byl 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 ami-
`nation 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
`com syrup, and high maltose com syrup can be utilized
`as well as the individual sugars listed above. These corn
`syrups may yield a mix of sugar components for Z. It
`should be understood that it is by no means intended to
`exclude other suitable raw materials. Z preferably will
`be selected from the group consisting of -CH2-
`(CHOH)n-CH20H, -CH(CH20HHCHOH)n-u(cid:173)
`CH20H, -CH2-(CHOHMCHOR')(CHOH)(cid:173)
`CH20H. 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-methy