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WO1992013059A1 - Pains de savon ameliores - Google Patents

Pains de savon ameliores Download PDF

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Publication number
WO1992013059A1
WO1992013059A1 PCT/US1992/000253 US9200253W WO9213059A1 WO 1992013059 A1 WO1992013059 A1 WO 1992013059A1 US 9200253 W US9200253 W US 9200253W WO 9213059 A1 WO9213059 A1 WO 9213059A1
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WIPO (PCT)
Prior art keywords
soap
fatty acid
weight
bar
reaction
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PCT/US1992/000253
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English (en)
Inventor
Francisco Antonio Pichardo
James Edward Kaleta
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The Procter & Gamble Company
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Publication of WO1992013059A1 publication Critical patent/WO1992013059A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen

Definitions

  • the present invention relates to soap bars, especially soap bars designed for personal hygiene and/or cosmetic use, which contain polyhydroxy fatty acid amides.
  • soap bars i.e., "toilet bars”
  • soap bars tend to undesirably form a type of soap/water gel, especially when stored in-use under circumstances where they can be contacted by water, e.g., in soap dishes, and the like, typically used in home lavatories.
  • the bar then softens and smears. Besides being unsightly, this leads to wastage of the bar, in-use.
  • One method of decreasing bar smear is by reducing the water content of the soap bar.
  • soap bars for personal hygiene use desirably have high lathering properties. Inappropriately adjusting the water content of otherwise standard soap bars to reduce wastage can impact nega ⁇ tively on lather properties.
  • Another way to decrease soap bar wastage is to employ highly saturated (i.e., low Iodine Value) fatty acid feedstocks in the soap.
  • low Iodine Value soaps lather poorly, yield bars which crack on storage and can have an undesirable gritty feel.
  • the present invention employs polyhydroxy fatty acid amides in combination with water-soluble fatty acid soaps, in the manner described hereinafter, to secure the above-mentioned objects.
  • the addition of the polyhydroxy fatty acid amides reduces the tendency of the soap bar to gel, thereby resulting in less smear and a longer-lasting bar. Furthermore, the polyhydroxy fatty acid amides boost lather and reduce bar cracking.
  • Hooker also describes nonionic surfactants of various types, and also nonionic lathering com- ponents which can include polyhydroxya ides of the formula
  • RC(0) contains from about 10 to about 14 carbon atoms
  • R x and R 2 each are H or C x -C 6 alkyl groups, said alky! groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6; column 4, line 11-28.
  • Hooker mentions stearoyl N-methyl glucamide and lauroyl N-methyl glucamide. See also, U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
  • N-alkyl gluca ides in detergent compositions has also been discussed.
  • U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and G.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
  • These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms.
  • These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.
  • U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz relates to aqueous detergent compositions containing the condensation reaction product of N-alkyl gluca ine and an aliphatic ester of a fatty acid.
  • the product of this reaction is said to be useable in aqueous detergent compositions without further purification.
  • PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth relates to a phiphilic compounds con ⁇ taining polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubil- izing membranes, whole cells, or other tissue samples, and for preparation of liposo es.
  • R'C0N(R)CH 2 R" and R"C0N(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.
  • European Patent 0 285 768 published October 12, 1988, H. Kelkenberg, et al, relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R 1 C(0)N(X)R 2 wherein R : is a c ⁇ " c i 7 (preferably C 7 -C 17 ) alkyl, R 2 is hydrogen, a C ⁇ C ⁇ (pref ⁇ erably Ci-Ce) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide.
  • the thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc.
  • anionic surfactants such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates
  • nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether,
  • Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified.
  • the N-polyhy ⁇ droxy alkyl fatty acid amides are said to have superior skin tolerance attributes.
  • U.S. Patent 2,982,737 issued May 2, 1961, to Boettner, et al, relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
  • glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al, which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxyalkyl-amine of the formula R : C(0)N(R 2 )CH 2 (CH0H) n - CH 2 0H, wherein R x is a Ci-C-j alkyl, R 2 is a C 10 -C 22 alkyl, and n is 3 or 4.
  • the N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.
  • U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl pol hydroxylalkyl compound of the formula R !
  • R x is a C 10 -C 22 alkyl
  • R 2 is a C 7 -C 2 ⁇ alkyl
  • R and R 2 total from 23 to 39 carbon atoms
  • Z is a polyhydroxyalkyl which can be -CH 2 (CHOH) m CH 2 ⁇ H where m is 3 or 4.
  • U.S. Patent 4,021,539 issued May 3, 1977, to H. M ⁇ ller, et al , relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which include compounds of the formula R_N(R)CH(CH0H) m R 2 wherein R is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R : but both cannot be H, and R 2 is CH 2 0H or COOH.
  • French Patent 1,360,018, April 26, 1963, assigned to Commer ⁇ cial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of amides of the formula RC(0)N(R x )G wherein R is a carboxylic acid functional ⁇ ity having at least seven carbon atoms, R x is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
  • German Patent 1,261,861, February 29, 1968, A. Heins relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(R ! )(R 2 ) wherein R is a sugar residue of glucamine, R ⁇ is a C 10 -C 20 alkyl radical, and R 2 is a C_-C 5 acyl radical.
  • G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carbox ⁇ ylic esters thereof that are said to be useful as chemical inter- mediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc.
  • the compounds are expressed by the formula N(R)(R ! )C(0)R 2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, Rj is a monoval- ent hydrocarbon radical, and -C(0)R 2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.
  • the present invention encompasses soap compositions in bar form, comprising: (a) from about 75% to about 85% by weight of a substantially water-soluble, non-lithium fatty acid soap;
  • Typical soap bars herein comprise from about 75% to about 85% by weight of a C 12 -C l ⁇ soap in the sodium, potassium, ammonium, or alkanol mmonium salt form; from about 1% to about 10% by weight of polyhydroxy fatty acid amide surfactant; and from about 8% to about 12% by weight of water.
  • the preferred polyhydroxy fatty acid amide surfactant is a C 12 -C X8 alkyl N-methyl glucamide, and the preferred fatty acid soap comprises the sodium salt of mixed C 12 -C 18 fatty acids.
  • Preferred bars according to this invention are characterized by a hardness value below about 3, more preferably below about 2, as measured by a "dry” (or, "as is") penetrometer test.
  • a highly preferred soap bar herein comprises: (a) about 75% to 85% of a sodium soap having an I.V. in the range of from about 25 to about 35;
  • the invention also encompasses a method for improving the hardness qualities of soap bars comprising substantially water- soluble, non-lithium fatty acid soap wherein said bar contains from about 8% to about 12% by weight of water, but without sub ⁇ stantial deleterious effect on the lather properties or tendency of said bars to crack on storage or use, by formulating said bars to comprise: (a) from about 8% to about 12% of water;
  • the bars herein can optionally also contain synthetic materials
  • Dish non-soap, non-polyhydroxy fatty acid amide, detergents typically at levels from about 0% to about 30% of the bar, depend- ing on the desires of the formulator.
  • the resulting mixture contains about 30% moisture.
  • the dried product noodles are then processed into bars using standard process equipment: premilling, amalgamator, milling, plodding, and stamping. Bars made in this manner can exhibit hardness grades ("dry") of about 2, by the penetrometer Test 1 described hereinafter. The following procedures can be used to measure the physical parameters of the bars of this invention.
  • Hardness Test Procedure The hardness of the bars prepared herein can be measured by the following procedure. In general, bars having a hardness value in the range below about 3, prefer- ably below about 2, in the first Test (Test 1) listed give good consumer value, acceptable smear, and the like. The first Test listed involves "pin" penetration of the "dry” bar, i.e., without contacting the bar with additional moisture other than the, roughly, 10% water present in the bar. In an alternate Test (Test 2; also shown below) the bar is first moistened. In the second Test procedure, penetration of a "ball” is used, and in this type of Test penetration scores below about 1.25, more preferably below about 1.0, are desirable.
  • - Cone has a 230.66 g weight on top of the cone shaft.
  • Press cone release lever hold for 10 seconds; release; raise cone arm; move to new point on bar surface; repeat process.
  • the reading will be an accumulative sum of the three penetrations.
  • the reading will be an accumulative sum of the penetrations.
  • ingredients used in the practice of this invention are known materials, and the ingredients per se and their individual methods of manufacture form no part of this invention. Rather, it is the combination of these ingredients to provide the composi ⁇ tions disclosed herein to achieve the desirable results that constitutes the invention herein. However, the ingredients are described below in order to assist the formulator.
  • Soaps - The soap ingredient herein is the well-known article of commerce, comprising the substantially water-soluble salts of fatty acids, typically C 12 -C l ⁇ fatty acids.
  • Such salts include the alkali, ammonium, alkanolammonium salts, and the like.
  • Sodium salts, potassium salts, triethanolammonium, ammonium, and the like, salts are mentioned here by way of exempl fication and not not by way of limitation.
  • Non-water soluble soaps especially lithium soaps, as well as insoluble calcium and magnesium soaps, are not used as the "soap" component of the bars of this inven- tion.
  • Fatty acids are available by synthetic processes, or, more typically, by base hydrolysis of fats and oils such as lard, palm oil, tallow, coconut oil, and the like. Coconut, tallow and palm oil fatty acids are mentioned by way of exemplification, but not limitation of fatty acid sources for typical soaps. Mixtures of fatty acids derived from various sources can be used.
  • the soaps used herein have a relatively low degree of unsaturation, i.e., have a relatively low Iodine Value, prefer- ably in the I.V.
  • low I.V. soaps can be prepared by hydrogenating fatty soap feedstocks, or by blending soap feedstocks with saturated fatty acids to lower the overall I.V. of the feedstock.
  • soaps prepared from the mixed tallow/stearic/coconut fatty acids noted hereinafter yield a very desirable bar, but this can be varied according to the desires, objectives and raw mater ⁇ ial resources of the formulator.
  • the water content of the bars herein is at least about 8% and typically ranges from about 8 to about 15, prefer- ably, about 10% by weight, of the finished bar.
  • the amount of water used by the formulator will depend on the softness of the bar that the formulator and user might find acceptable, the chain length of the fatty acid soaps, the amount of polyhydroxy fatty acid amide used in the bar, and the like. Such matters can be adjusted, as a matter of routine.
  • Electrolytes - The bar herein will optionally, but prefer ⁇ ably, contain an electrolyte. Electrolytes are commonly added to soap bars to cause the soap to be in the form of what is commonly referred to as "neat" phase. The selection of electrolytes for use in soap bars is a matter of discretion of the formulator, but typical, inexpensive, water-soluble toxicologically-acceptable electrolytes include a wide variety of organic or, more typically, inorganic salts such as alkali metal halides, sulfates, phos ⁇ phates, and the like.
  • the electrolyte need not comprise more than about 2%, and more preferably comprises from about 0.2% to about 0.6%, by weight of the bar.
  • the bars herein can optionally contain various additional ingredients of the type typically used in toilet and cosmetic bars.
  • Such ingredients can typically range from about 0.1% to about 15% by weight of the bars, depending on the objectives of the formulator.
  • One additional type of optional ingredient used in the bars herein includes the synthetic detergents such as the sulfated and sulfonated of C 12 -C l ⁇ alcohols, alkyl benzene, and the like.
  • Nonionic synthetic detergents such as the C 12 -C 18 polyethoxylates, C 12 -C 18 alkyl phosphates, zwitterionics, cationics, amine oxides, and the like, can be used.
  • Such synthetic detergents are well- known, and reference can be made to McCutcheon's Index or other texts for standard listings. If used, such syndets conveniently comprise about 2% to about 15% by weight of the bar.
  • R-l The reaction for the preparation of the polyhydroxyamines which are used to prepare the polyhydroxy fatty acid amide sur ⁇ factants employed herein can be termed the "R-l" reaction, and is illustrated by the formation of N-methylglucamine, wherein R 1 is methyl.
  • the reactants, solvents and catalysts used in the R-l reac ⁇ tion are all well-known materials which are routinely available from a variety of commercial sources. The following are nonlimit ⁇ ing examples of materials which can be used herein.
  • Amine Material - The amines useful in the R-l reaction herein are primary amines of the formula R ⁇ Hz, wherein R 1 is, for example, alkyl, especially C x -C 4 alkyl, or Ci-C 4 hydroxyal yl . Examples include methyl, ethyl, propyl , hydroxyethyl , and the like.
  • Nonlimiting examples of amines useful herein include methyl amine, ethyl amine, propyl amine, butyl amine, 2-hydroxypropyl amine, 2-hydroxyethyl amine; methyl amine is preferred. All such amines are sometimes jointly referred to as "N-alkyl amines”.
  • Polvhvdroxy Material - A preferred source of polyhydroxy materials useful in the R-l reaction comprises reducing sugars or reducing sugar derivatives. More specifically, reducing sugars useful herein include glucose (preferred), maltose, fructose, maltotriose, xylose, galactose, lactose, and mixtures thereof.
  • Catalyst - A variety of hydrogenation catalysts can be used in the R-l reaction. Included among such catalysts are nickel (preferred), platinum, palladium, iron, cobalt, tungsten, various hydrogenation alloys, and the like.
  • a highly preferred catalyst herein comprises "United Catalyst G49B" a particulate Ni catalyst supported on silica, available from United Catalysts, Inc., Louisville, Kentucky.
  • Solvent - Formation of the adduct in the R-l process is carried out using an excess of the amine as the solvent.
  • the excess amine also is used in the subsequent reaction with hydrogen.
  • the amine can be replaced with an alcohol, such as methanol, for the hydrogen reaction.
  • Typical examples of solvents useful herein in the formation of the amine-sugar adduct include methyl amine, ethyl amine, and hydroxyethyl amine; methyl amine is preferred; methyl amine/water solvent can also be used.
  • General R-l Reaction Conditions - Reaction conditions for the R-l reaction are as follows.
  • Adduct formation The reaction time used for adduct formation will typically be on the order of 0.5-20 hours, depending somewhat on the reaction temperature chosen. In general, lower reaction temperatures in the range of O'C-80'C require longer reaction times, and vice-versa . In general, over the preferred 30 * C-60 ⁇ C reaction temperature range, good adduct yields are achieved in 1-10 hours. Generally good adduct formation is achieved at about a 4:1 to 30:1 mole ratio of amine:sugar. Typical sugar reactant concentrations in the amine solvent are in the 10%-60% (wt.) range. Adduct formation can be carried out at atmospheric or superatmospheric (preferred) pressures. (b) Reaction with Hydrogen - The reaction with hydrogen can typically be run, for example, at temperatures of
  • step (b) can be dried by solvent/water stripping, or by crystallization, trituration, or by means of effective drying agents.
  • Anhydrous glucose (36.00 g; Aldrich Chemical Company) is weighed into a glass liner.
  • the glass liner is placed into a dry-ice bath and methyl amine gas (68.00 g; Matheson) is condensed into the glass liner.
  • the liner is then loaded into a rocking autoclave (500 ml capacity).
  • the autoclave is heated to 50 * C and rocked for 5 hours at 50*C under 600 psig nitrogen to form the adduct (N-methyl lucosylamine).
  • the reaction is then cooled in a dry-ice bath.
  • the autoclave is then vented cold.
  • Example II The process of Example I is repeated in a stirred autoclave fitted with a fritted exit filter, a triple impeller stirrer, outlet and inlet tubes and a baffle.
  • Reagents and reaction conditions for the preparation of N-methyl glucamine are as follows: 15 g of 20% G49B catalyst (Ni/silica; United Catalyst) 0 and 75 g glucose powder (Aldrich, Lot 07605LW) are slurried in 160 mis methanol and pretreated with H 2 for one hour (50 * C). The mixture is then cooled and the methanol is removed by pressure.
  • the reactor is cooled to less than 5"C and charged with 76 is of liquid methyl amine. 5
  • the reaction mixture is slowly heated to 60 * C over 46 minutes at 250 psi hydrogen and sampled. Heating is continued at 60"C for 20 minutes and sample 2 is taken. Heating is continued at 60 * C for 46 minutes (sample 3) and then at 60 * C for 17 minutes (sample 4).
  • the reaction mix is heated to 70 * C for an additional 33 0 minutes (sample 5). Total reaction time is 2.7 hours.
  • the dried product is 93.2% N-methyl glucamine (GC analysis).
  • the polyhydroxyamine products of the aforesaid R-l reaction are desirable and can be further employed in an amide-forming reaction which is desig- 5 nated herein as the "R-2" reaction.
  • R-2 amide-forming reaction
  • a typical R-2 amide-forming reaction herein can be illustrated by the formation of lauroyl N-methyl glucamide, as follows. methanol R*C00Me + MeN(H)CH 2 (CH0H) 4 CH 2 0H Q methoxide
  • an overall reaction for preparing polyhydroxy fatty acid amide surfactants comprises: 5 (a) reacting a reducing sugar (preferably glucose) or reducing sugar derivative with an amine reactant (preferably methyl amine) in an amine solvent (preferably, methyl amine) to provide an adduct ; (b) reacting said adduct from step (a) dissolved in said amine solvent with hydrogen in the presence of a metal catalyst;
  • step (d) reacting said substantially anhydrous polyhydroxya ine product from step (c) with a fatty acid ester in an organic hydroxy solvent (preferably, methanol or propylene glycol) in the presence of a base catalyst to form the polyhydroxy fatty acid amide surfactant (preferably, at a temperature below about 100'C); and
  • a fatty acid ester in an organic hydroxy solvent (preferably, methanol or propylene glycol) in the presence of a base catalyst to form the polyhydroxy fatty acid amide surfactant (preferably, at a temperature below about 100'C);
  • step (e) optionally, when the reaction step (d) is essentially complete, removing said solvent used in step (d).
  • R 1 is H, C x -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy propyl, or a mixture thereof, preferably ⁇ alkyl, more preferably C x or C 2 alkyl, most preferably C x alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl moiety, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, most preferably straight chain C n -C X7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydrox hydrocarbyl 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.
  • high dextrose corn 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 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 -CH 2 -(CH0H) n -CH 2 0H, -CH(CH 2 0H)-(CH0H) n . 1 -CH 2 0H, -CH 2 -(CH0H) 2 (CH0R')(CH0H)-CH 2 0H, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CH0H) 4 -CH 2 0H.
  • R 1 can be, for example, N-methyl, N-ethyl , N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl .
  • R 2 -CO-N ⁇ can be, for example, cocamide, steara ide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowa ide, etc.
  • Z can be 1-deoxyglucityl , 2-deoxyfructityl , 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl , 1-deoxymannityl , 1-deoxymalto- triotityl, etc.
  • Reactants - Various fatty esters can be used in the R-2 reaction, including mono-, di- and tri-esters (i.e., triglycer- ides). Methyl esters, ethyl esters, and the like are all quite suitable.
  • the polyhydroxyamine reactants include reactants available from the above-described R-l reaction, such as N-alkyl and N-hydroxyalkyl polyhydroxyamines with the N-substituent group such as CH 3 -, C 2 H 5 -, C 3 H 7 -, H0CH 2 CH 2 -, and the like.
  • Polyhy- droxyamines available from the R-l reaction are preferably not contaminated by the presence of residual amounts of metallo hydrogenation catalysts, although a few parts per million [e.g., 1-20 ppm] can be present.) Mixtures of the ester and mixtures of the polyhydroxyamine reactants can also be used.
  • Catalysts - The catalysts used in the R-2 reaction are basic materials such as the alkoxides (preferred), hydroxides (less preferred due to possible hydrolysis reactions), carbonates, and the like.
  • Preferred alkoxide catalysts include the alkali metal C ⁇ -C 4 alkoxides such as sodium methoxide, potassium ethoxide, and the like.
  • the catalysts can be prepared separately from the reaction mixture, or can be generated in situ using an alkali metal such as sodium. For in situ generation, e.g., sodium metal in the methanol solvent, it is preferred that the other reactants not be present until catalyst generation is complete.
  • the catalyst typically is used at a level of about 5 mole % of the ester reactant. Mixtures of catalysts can also be used.
  • Solvents The organic hydroxy solvents used in the R-2 reaction include, for example, methanol, ethanol, propanol, iso-propanol, the butanols, glycerol, 1,2-propylene glycol, 1,3-propylene glycol, and the like. Methanol is a preferred alcohol solvent and 1,2-propylene glycol is a preferred diol solvent. Mixtures of solvents can also be used.
  • General R-2 Reaction Conditions It is preferred to prepare the desired products while minimizing the formation of cyclized by-products, ester amides and color bodies.
  • Reaction temperatures below about 135 * C are used to achieve this objective, especially in batch processes where reaction times are typically on the order of about 0.5-2 hours, or even up to 6 hours. Somewhat higher temperatures can be tolerated in continu ⁇ ous processes, where residence times can be shorter.
  • Example III The concentration ranges of the reactants and solvent in Example III provide what can be termed a "70% concen- trated" (with respect to reactants) reaction mixture. This 70% concentrated mixture provides good results, in that high yields of the desired polyhydroxy fatty acid amide product are secured rapidly. Indeed, indications are that the reaction is substan ⁇ tially complete within one hour, or less. The consistency of the reaction mixture at the 70% concentration level provides ease of handling.
  • Example III The product of Example I (9.00 g, 0.0461 moles, N-methyl- glucamine) is combined with 8.22 g methanol anhydrous in a round bottom flask fitted with condenser, drying tube and argon blanket. The reaction methanol and N-methylglucamine are heated to reflux for 15 minutes. Sodium methoxide (0.1245 g, 0.0023 moles, Aldrich Chemical Company) and methyl ester (10.18 g, 0.0461 moles, Procter & Gamble CE1270, includes C 12 -C 18 fatty acid esters) are added and reaction continued at reflux for 3 hours. Methanol is then removed under reduced pressure to give essentially colorless white product.
  • EXAMPLE IV An overall process at the 80% reactant concentration level for the amide synthesis is as follows. A reaction mixture consisting of 84.87 g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75 g. N-methylglucamine per Example I, above, 1.04 g. sodium methoxide and a total of 39.96 g. methyl alcohol ⁇ ca. 20% by wt. of reaction mixture) is used. The reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and mechanical stir ⁇ ring blade. The N-methyl glucamine/methanol is heated with stirring under argon (reflux).
  • source Procter & Gamble methyl ester CE1270
  • the reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and mechanical stir ⁇ ring blade.
  • the N-methyl glucamine/methanol is heated with stirring under argon (reflux).
  • Example V The process of Example IV is repeated at the 90% reactant level for the polyhydroxy fatty acid amide synthesis step. Levels of undesirable by-products are extremely low, and reaction is essentially complete at 30 minutes. In an alternate mode, the reaction can be initiated at a 70% reactant concentration, for example, and methanol can be stripped during the course of the reaction and the reaction taken to completion.
  • Example VI The process of Example III is repeated in ethanol (99%) and 1,2-propylene glycol (essentially dry), respectively, with good product formation.
  • a solvent such as 1,2-propylene glycol is used in the R-2 step, with methanol stripping throughout the process.
  • the resulting surfactant/glycol mix can be used directly in a detergent composition.
  • EXAMPLE VII Using a stirred autoclave and procedure per Example II, 15 g of the 649B catalyst, glucose powder (75 g; Aldrich) and 160 mis methanol are slurried and treated with H 2 to remove oxide from the catalyst surface. Methanol is removed. 80 mis (52.8 g) of methyl amine are added to the glucose/catalyst mixture at below 5 * C, and 22 mis water are added at room temperature.
  • the reaction mixture is heated to 70'C in 34 minutes and held at 70'C for 40 minutes, during the hydrogenation.
  • the H 2 0/methyl amine solution of the reaction product is blown out of the reactor through the frit (removes catalyst) and dried to yield the
  • N-methylglucamine product When using the mixed amine/water solvent, weight ratios of amine (especially, methyl amine) and water in a range of from about 10:1 to about 1:1 are typically employed.
  • the R-l reaction product substantially free from water (preferably, less than about 1%, more preferably, less than about 0.3% by weight of water) can then be used in the R-2 reaction to prepare polyhydroxy fatty acid amides, as described above.
  • N-methyl polyhydroxy amines such as N-methyl glucamine
  • their fatty acid amide derivatives using fatty methyl esters variations are available.
  • reducing sugars such as fructose, galactose, mannose, maltose and lactose, as well as sugar sources such as high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, and the like, can be used to prepare the polyhydroxyamine material (i.e., to replace glucamine) of the reaction.
  • fats and oils can be used herein in place of the fatty esters exemplified above.
  • fats and oils such as soybean oil, cottonseed oil, sunflower oil, tallow, lard, safflower oil, corn oil, canola oil, peanut oil, fish oil, rapeseed oil, and the like, or hardened (hydrogenated) forms thereof, can be used as the source of tri- glyceride esters for use in the present process.
  • the present process is particularly useful when preparing the longer-chain (e.g., C l ⁇ ) and unsaturated fatty acid polyhydroxy amides, since the relatively mild reaction temperatures and conditions herein afford the desired products with minimal by-product formation.
  • a pre-formed portion of the polyhydroxy fatty acid amide surfactant can be used to assist initiation of the R-2 amid ⁇ -forming reaction when triglycerides or the longer-chain methyl esters are used as reactants.
  • use of propylene glycol, or glycerine, or preformed mono esters thereof can assist in initiation of the R-2 reaction, as well.
  • Surfactant yields in the R-2 process can be increased by simply storing the solidified product (which contains some minor amount of entrained solvent and reactants) e.g., at 50*C, for a few hours after removal from the reaction vessel. Storage in this manner apparently allows the last fraction of unreacted starting materials to continue to form the desired polyhydroxy fatty acid amide surfactant. Thus, yields can be increased appreciably, i.e., to a high degree of completion, which is an important consideration in large-scale industrial processes.
  • the following illustrates the use of the above-described surfactant products of the overall R-l plus R-2 process to prepare bar soap compositions in the manner of this invention. These examples are not intended to be limiting, since a wide variety of surfactants, perfumes and optional other ingredients well-known to bar soap for ulators can optionally be used in such compositions, all at conventional usage levels.
  • a typical soap bar composition is as follows. Ingredient Percent fwt.) Fatty acid soap* 83.75
  • Example VIII The bar of Example VIII is modified by reducing the soap level to 76% and increasing the alkyl glucamide (made per Example IV) level to 10%. A softer bar is thereby secured.
  • EXAMPLE X The bar of Example VIII is modified by increasing the soap level to 85% and decreasing the alkyl glucamide surfactant level to 2%. A harder bar is thereby secured.
  • a soap/syndet mixed bar is as follows. Ingredient Percent fwt.l

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des pains de savon contenant des amides d'acide gras polyvalents présentent de bonnes qualités d''enduction', une bonne dureté ainsi que de bonnes propriétés de moussage. Les pains présentent également une tendance réduite à la fragmentation. L'invention concerne également des pains comprenant du savon et des matières telles que le glucamide N-méthylique C12-C18.
PCT/US1992/000253 1991-01-29 1992-01-21 Pains de savon ameliores WO1992013059A1 (fr)

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US64536191A 1991-01-29 1991-01-29
US645,361 1996-05-13

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WO1992013059A1 true WO1992013059A1 (fr) 1992-08-06

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CN (1) CN1031286C (fr)
AR (1) AR244794A1 (fr)
AU (1) AU1200692A (fr)
IE (1) IE920277A1 (fr)
MA (1) MA22404A1 (fr)
MX (1) MX9200341A (fr)
MY (1) MY108165A (fr)
NZ (1) NZ241423A (fr)
PH (1) PH30035A (fr)
PT (1) PT100070A (fr)
TR (1) TR26603A (fr)
TW (1) TW214567B (fr)
WO (1) WO1992013059A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2703993A1 (fr) * 1993-04-15 1994-10-21 Oreal Utilisation en cosmétique de dérivés lipophiles des amino déoxyalditols, compositions cosmétiques les contenant, et nouveaux carbamates d'alkyle.
DE4331297A1 (de) * 1993-09-15 1995-03-16 Henkel Kgaa Stückseifen
WO1995007340A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Composition en barre contenant un tensioactif a base d'amide d'acides gras n-aryloxy polyhydroxy
US5616746A (en) * 1993-04-15 1997-04-01 L'oreal Use in cosmetics of lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and novel alkyl carbamates
US5736503A (en) * 1992-11-30 1998-04-07 The Procter & Gamble Company High sudsing detergent compositions with specially selected soaps
EP0934376A1 (fr) * 1996-07-02 1999-08-11 Henkel Corporation Pains de savons contenant un abrasif
WO2007017619A1 (fr) * 2005-08-10 2007-02-15 Appaya Raghunath Naik Formulations detergentes a base de savon et d'acide gras de n-methyle glucamide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312627A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
US3576749A (en) * 1969-02-06 1971-04-27 Procter & Gamble Soap toilet bars having improved smear characteristics
EP0220676A1 (fr) * 1985-10-29 1987-05-06 Süddeutsche Zucker-Aktiengesellschaft Amides d'acides gras d'aminopolyols comme tensio-actifs non ionogènes
EP0222525A2 (fr) * 1985-10-29 1987-05-20 The Procter & Gamble Company Composition pour la toilette et procédé
EP0285768A1 (fr) * 1987-04-08 1988-10-12 Hüls Aktiengesellschaft Utilisation de N-polyhydroxyalkyl d'amides d'acides gras comme agents épaississants pour systèmes tensio-actifs liquides aqueux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312627A (en) * 1965-09-03 1967-04-04 Procter & Gamble Toilet bar
US3576749A (en) * 1969-02-06 1971-04-27 Procter & Gamble Soap toilet bars having improved smear characteristics
EP0220676A1 (fr) * 1985-10-29 1987-05-06 Süddeutsche Zucker-Aktiengesellschaft Amides d'acides gras d'aminopolyols comme tensio-actifs non ionogènes
EP0222525A2 (fr) * 1985-10-29 1987-05-20 The Procter & Gamble Company Composition pour la toilette et procédé
EP0285768A1 (fr) * 1987-04-08 1988-10-12 Hüls Aktiengesellschaft Utilisation de N-polyhydroxyalkyl d'amides d'acides gras comme agents épaississants pour systèmes tensio-actifs liquides aqueux

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5736503A (en) * 1992-11-30 1998-04-07 The Procter & Gamble Company High sudsing detergent compositions with specially selected soaps
WO1994024097A1 (fr) * 1993-04-15 1994-10-27 L'oreal Utilisation en cosmetique de derives lipophiles des amino deoxyalditols, compositions cosmetiques les contenant, et nouveaux carbamates d'alkyle
US6210691B1 (en) 1993-04-15 2001-04-03 L'oreal Cosmetics of lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and novel alkyl carbamates
FR2703993A1 (fr) * 1993-04-15 1994-10-21 Oreal Utilisation en cosmétique de dérivés lipophiles des amino déoxyalditols, compositions cosmétiques les contenant, et nouveaux carbamates d'alkyle.
US6001376A (en) * 1993-04-15 1999-12-14 L'oreal Lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and novel alkyl carbamates
US5616746A (en) * 1993-04-15 1997-04-01 L'oreal Use in cosmetics of lipophilic derivatives of amino deoxyalditols, cosmetic compositions containing them, and novel alkyl carbamates
WO1995007340A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Composition en barre contenant un tensioactif a base d'amide d'acides gras n-aryloxy polyhydroxy
US5712235A (en) * 1993-09-15 1998-01-27 Henkel Kommanditgesellschaft Auf Aktien Bar soaps
WO1995007975A1 (fr) * 1993-09-15 1995-03-23 Henkel Kommanditgesellschaft Auf Aktien Savonnette
DE4331297A1 (de) * 1993-09-15 1995-03-16 Henkel Kgaa Stückseifen
EP0934376A1 (fr) * 1996-07-02 1999-08-11 Henkel Corporation Pains de savons contenant un abrasif
EP0934376A4 (fr) * 1996-07-02 1999-12-15 Henkel Corp Pains de savons contenant un abrasif
WO2007017619A1 (fr) * 2005-08-10 2007-02-15 Appaya Raghunath Naik Formulations detergentes a base de savon et d'acide gras de n-methyle glucamide

Also Published As

Publication number Publication date
CN1065678A (zh) 1992-10-28
NZ241423A (en) 1995-07-26
AR244794A1 (es) 1993-11-30
TW214567B (fr) 1993-10-11
MA22404A1 (fr) 1992-10-01
PT100070A (pt) 1993-06-30
AU1200692A (en) 1992-08-27
IE920277A1 (en) 1992-07-29
CN1031286C (zh) 1996-03-13
TR26603A (tr) 1995-03-15
PH30035A (en) 1996-11-08
MY108165A (en) 1996-08-30
MX9200341A (es) 1994-03-31

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