EP1135362A1 - Tensioactifs d'ester cationique utilises dans des formulations liquides et pulverulentes - Google Patents

Tensioactifs d'ester cationique utilises dans des formulations liquides et pulverulentes

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Publication number
EP1135362A1
EP1135362A1 EP99962973A EP99962973A EP1135362A1 EP 1135362 A1 EP1135362 A1 EP 1135362A1 EP 99962973 A EP99962973 A EP 99962973A EP 99962973 A EP99962973 A EP 99962973A EP 1135362 A1 EP1135362 A1 EP 1135362A1
Authority
EP
European Patent Office
Prior art keywords
carbons
alkyl
formulation
group
independently
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP99962973A
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German (de)
English (en)
Inventor
Pierre M. Lenoir
Kees Delcour
Marinus Meertens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
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Dow Chemical Co
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Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP1135362A1 publication Critical patent/EP1135362A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/08—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the hydroxy groups esterified by a carboxylic acid having the esterifying carboxyl group bound to an acyclic carbon atom of an acyclic unsaturated carbon skeleton
    • 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
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations

Definitions

  • the present invention concerns the use of a particular class of compositions in detergent applications, especially laundry applications and cleaners.
  • the present invention relates to the use of quatemized alkanol amine ester compositions wherein the ester is based on a secondary or tertiary alcohol, and/or the use of a quatemized alkoxylated alkanol amine ester in detergent, cleaner, personal care, or fabric softening applications.
  • Surfactant systems comprising cationic ester surfactants have been widely described for their use in detergent applications. These compounds comprise at least one cationically charged group, usually an ammonium-based compound and at least one ester group.
  • WO-A-97/03160 indicates the benefits of having cationic ester surfactants in laundry detergents. These benefits include superior greasy cleaning and improved antiredeposition of soils during the wash process.
  • CET cationic ester surfactants
  • WO 97/31889 also discloses the problem with this broad class of compounds of lacking hydrolytic stability.
  • this reference states, "The Applicants have now found that a problem with the use of certain cationic ester surfactants is the tendency for the ester linkage to hydrolytically cleave, thereby breaking up the surfactant molecule, under the wash conditions of a typical laundry or dishwashing method. Surfactant performance in the wash is thereby compromised.”
  • the solution that WO 97/31889 proposes is to separate the ester group from the cationically charged group by a spacer group of at least three atoms. Such spacer groups add expense to the composition, however, and so is less than an ideal solution.
  • esterifying secondary or tertiary alcohols rather than primary alcohols leads to cationic ester surfactants which have vastly improved hydrolytic stability over their primary alcohol counterparts.
  • the Applicants have also discovered that the introduction of oxide sequences also provides improved stability. This improved stability diminishes the rate of the break up of the surfactant which occurs in the wash environment and also allows the surfactant to be used in liquid detergent formulations.
  • compositions of the present invention exhibit surprisingly high hydrolytic stability over a wide pH range, have generally unexpectedly low melting points, are more compatible with detergents, softeners, cleaners and personal care ingredients and they can be more easily handled either in the diluted form or formulated as stable liquid concentrates as compared to corresponding cationic ester surfactant having been esterified from primary alcohols. Accordingly, these compounds are advantageously used in such applications as detergents, softeners, cleaners and personal care items.
  • compositions suitable for use in the present invention correspond to the general formula:
  • R is an alkyl or alkenyl group having 2 to 30 carbons
  • R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , R 0 and R 11 are independently in each occurrence H or an alkyl group preferably having from 1 to 6 carbons
  • n and m are independently in each occurrence a number equal to 1 or greater, preferably 1 to 5
  • z is 0 or greater, preferably 0 to 10
  • R 5 and R 6 are independently an alkyl having from 1-6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group
  • R 7 is an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons, optionally substituted with an alkyl group, or HOCHR 12 CH 2 -, wherein R 12 is H or an alkyl group having 1 to 4 carbons
  • X ' is an inorganic or organic acid anion; with the proviso that when z is
  • R 5 , R 6 and R 7 are all alkyl then each has less than 3 carbons. It is preferred that R have from 4 to 24 carbon atoms, and more preferred that R have from 7 to 22 carbon atoms.
  • the R group may be straight or branched, and may have different levels of saturation. Generally, it is preferred that the R group have an Iodine value less than 140. Iodine values can be calculated by ways known in the art. For some applications, such as for use in clear transparent concentrated fabric softeners, it is generally preferred that the R group have Iodine values greater than 20, but in other applications, such as detergents, Iodine values less than 20, including fully saturated R groups can be advantageously used.
  • "clear" has the generally accepted meaning within the art but especially means transparent, such that vision is not significantly hindered when looking through a 10 cm, preferably 15 cm and most preferably 30 cm thick cell containing the formulation.
  • n and m be equal to 1 , especially in those moieties where R 3 or R 4 (or R 10 or R 1 ) is an alkyl group. It is also preferred that R 1 , R 2 , R 8 and R 9 are H. It is also generally preferred that not both R 3 and R and not both R 10 and R 11 are alkyl groups in the same moiety. Furthermore it is preferred that when R 3 , R 4 , R 0 or R 1 is an alkyl group, it is an alkyl group having 1 or 2 carbons.
  • n and R 1 , R 2 , R 3 and R 4 are such that the number of carbon atoms between N and the oxygen atom directly connected to CR 3 R 4 , including branching, is no more than 6.
  • m and R 8 , R 9 , R 10 and R 11 are such that the number of carbon atoms between oxygen atoms, including branching, is no more than 6.
  • z be from 0 to 10. Detergency properties can be optimized when z is 0, however using alkanolamines where z is greater than 0 facilitates the use of slightly longer carboxylic acids in the esterification step. If z is 1 then it is preferred that R 3 , R ⁇ R 10 and R 11 are not all H.
  • the alkanolamine is formed by alkoxylating a an alkyl amine with an alkylene oxide, where the alkyl amine corresponds to the formula:
  • R 5 and R 6 are as defined above (that is, independently an alkyl having from 1 to 6 carbon atoms, a cycloalkyl having 6 carbon atoms, or an aryl group), and the alkylene oxide corresponds to the formula C y H 2y O, where y is from 2 to 18, preferably 2 to 6.
  • Preferred alkyl amines include dimethyl amine, diethy! amine and methyl ethyl amine.
  • Preferred alkylene oxides include ethylene oxide, propylene oxide and butylene oxide, or mixtures thereof. Propylene oxide and butyiene oxide are the most preferred oxides, especially in those compositions in which z is 0. Where oxide sequences are added (that is, in those species where z is not 0) the oxides may be added by either block or random addition.
  • this alkoxylation reaction process may be carried out in the presence of an alkaline catalyst, such as sodium, potassium, calcium, barium and strontium hydroxide, in an amount of from 0.01 to 5, preferably 0.1 to 0.5, percent by weight based on the total weight of the mixture at the completion of the reaction.
  • an alkaline catalyst such as sodium, potassium, calcium, barium and strontium hydroxide
  • the alkoxylation reaction is carried out at an elevated temperature, preferably at a temperature from 50°C to 200°C, more preferably from 80°C to 120°C and a pressure of from 1 to 80 bars.
  • the alkaline catalysts suitable for use in this reaction are well known to a person skilled in the art.
  • the catalyst is removed by a suitable method, such as by filtration over an absorbing clay, for example, magnesium silicate, or neutralized with an inorganic acid such as, for example, hydrochloric acid, or an organic acid such as, for example, acetic acid.
  • an excess of an acid can be used, so that the excess of the acid can serve as a catalyst in the subsequent reaction step. It is advantageous to carry out the alkoxylation reaction in the presence of a defoaming agent.
  • the esterification reaction comprises contacting the alkanolamine with a carboxylic acid (or a mixture of carboxylic acids) under conditions sufficient to cause at least a portion of the carboxylic acid to react with at least a portion of the OH groups on the alkanolamine so as to form esters.
  • the carboxylic acid corresponds to the formula RCOOH, where R is an alkyl group having 1 to 30 carbons. It is preferred that R have from 4 to 24 carbon atoms, and more preferred that R have from 7 to 22 carbon atoms.
  • the R group may be straight or branched, and may have different levels of saturation. Generally, it is preferred that the R group have an Iodine value less than 140. Iodine values can be calculated by ways known in the art.
  • the R group have Iodine values greater than 20, but in other applications, Iodine values less than 20, including fully saturated R groups can be advantageously used.
  • carboxylic acids useful in the esterification reaction include valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid, and the branched isomers thereof (isovaleric acid, for example), or the unsaturated isomers thereof (for example, oleic acid).
  • These fatty acids are well-known to the person of ordinary skill in the art.
  • the esterification reaction conveniently is carried out at an elevated temperature, preferably at a temperature from 50°C to 250°C, more preferably from 180°C to 220°C, and reduced pressure, preferably from 1 to 500 mbar, more preferably from 20 to 200 mbar.
  • the carboxylic acid may be added in the range of 0.5 to 5 moles of carboxylic acid per mole of alkanolamine. It is preferred that the carboxylic acid be added at approximately an equimolar ratio to the alkanolamine, although slight excesses of carboxylic acid may help speed the reaction.
  • the esterified alkanolamines can then be quatemized by contacting the esterified alkanolamines with a composition corresponding to the formula R 7 X, under conditions sufficient to cause at least a portion of the esterified alkanolamines to form a quatemized product.
  • R 7 in the above formula is an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons, optionally substituted with an alkyl group, or HOCHR 12 CH 2 -, wherein R 12 is H or an alkyl group having 1 to 4 carbons; and X is an inorganic or organic acid anion.
  • the quatemization reaction is preferably carried out at a ratio of from 0.1 to 20 moles R 7 X per mole of esterified alkanolamine, at a temperature of from 30°C to 150°C, and a pressure of from 1 to 50 bars.
  • Any known quaternizing agent can be used as the R 7 X compound.
  • Suitable quaternizing agents of formula R 7 X include alkyl halides, dialkyl sulfates, and trialkyl phosphates.
  • Preferred alkyl halides include methyl chloride, ethyl chloride, methyl bromide, and ethyl bromide; preferred dialkyl sulfates include dimethyl sulfate, and diethyl sulfate, and preferred trialkyl phosphates include trimethyl phosphate and triethyl phosphate. It is advantageous to carry out the quatemization reaction in the presence of a defoaming agent. It can also be advantageous to carry out the quatemization reaction in the presence of an additive which can lower the melting point of the reaction mixture, as is known in the art. These additives can be added at any stage of the reaction, including after the reaction has been completed.
  • additives at different stages of the reaction, for example one additive during the quatemization reaction and then either more of the same additive or a new additive after the quatemization reaction has finished.
  • additives can be especially useful when the quatemized product is not a liquid at room temperature.
  • Suitable additives include materials such as water, isopropanol, propanediol, dipropylene glycol, PEG, PPG, alkoxylated fatty acids and alcohols having more than 3 carbons in the fatty chain, glycol ether solvents such as DOWANOLTM P and E series, diether solvents such as PROGLYDETM DMM, tetrahydrofuran, methanol, ethanol, hexanediol, and acetone, and mixtures thereof. If such additives are used it is preferred that the final reaction mixture contain at least 70 percent by weight, more preferably at least 75 percent by weight and most preferably 80 percent by weight of the cationic ester surfactant.
  • hydrolytically stable means that less than 30 percent, preferably less than 20 percent, of the composition hydrolyzes after 4 weeks from a 5 percent aqueous solution having a pH value of 4, at a temperature of 50°C. It should be understood that the extent of hydrolysis defined above is valid for a value of pH 4 and that hydrolysis extent would decrease with decreasing pH and increase with increasing pH.
  • the improved hydrolytic stability of the compositions of the present invention allow them to be used in liquid or gel detergent, softergent, cleaner, personal care, or softening formulations. Furthermore, the improved hydrolytic stability facilitates the perseverance of the material in the wash environment itself, and so makes the compositions useful in solid formulations such as granules, powders and tablets, as well.
  • compositions of the present invention are compatible even with detergent ingredients which are normally not compatible with known cationic ester surfactants without the presence of special additives.
  • the formulations of the present invention can also incorporate one or more known ingredients commonly used in detergent, fabric softening, personal care or cleaner formulations.
  • Such materials are known in the art (for example many are described in WO 97/31889 and WO 98/35002) and include, but are not limited to the following:
  • Enzymes and Enzyme Stabilizers - Enzymes can be included for various fabric cleaning purposes.
  • suitable enzymes include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • the enzymes may be of any suitable origin, such as vegetable, animal, bactericidal, fungal and yeast origin.
  • the enzymes used may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions. Any water-soluble calcium or magnesium salt can be used as a source of calcium or magnesium ions.
  • a wide range of useful enzyme and enzyme stabilizer materials are described in WO-A- 95/19951 and WO-A-96/21715, and EP-A-0579295 and EP-A-0583536.
  • Bleaching Agents and Bleach Activators Any known bleaching agent used in fabric or paper treatment applications can be used. Nonlimiting examples of suitable bleaching agents include oxygenated bleaches, percarboxylic acid bleaches, peroxygen bleaches and mixtures thereof. Bleach activator can also be used. Various nonlimiting examples of useful bleaching agents and bleach activators are given in WO-A-95/19951.
  • Suitable builders include, but are not limited to, phosphates, polyphosphates, silicates, aluminosilicates, phosphonates, carboxylates, zeolites and succinates.
  • suitable builders are described in WO-A-95/19951 and EP-A-0579295, and EP-A-0580245.
  • Soil Release Agents Any known polymeric soil release agent used in laundry cleaning formulations can be used.
  • Polymeric soil release agents include, but are not limited to, the compounds having: (i) at least one nonionic hydrophilic component consisting essentially of (a) polyoxyethylene segments with a degree of polymerization of at least 2, or (b) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, or (c) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, (d) cellulosic derivatives such as hydroxyether cellulosic polymers, (e) copolymeric blocks of terephthalate with polyethylene oxide or polypropylene oxide.
  • Nonlimiting examples of useful soil release agents are given in WO-A-95/04802, WO-A-93/23510 and WO-A-93/25648.
  • Chelating agents Any known chelating agent is suitable for use. Suitable chelating agents include, but are not limited to, amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. It is believed that the benefit of the chelating materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. Nonlimiting examples of suitable chelating agents are described in WO-A-95/19951 and WO-A-96/21715.
  • Clay Soil Removal/Anti-Redeposition Agents Any water-soluble alkoxylated amines having clay soil removal and anti-redeposition properties normally used in granular or liquid detergents can be used. Nonlimiting examples of useful clay soil removal/anti-redeposition agents are described in WO-A- 95/19951.
  • Dispersing Agents - Suitable dispersing agents are polymeric dispersing agents such as, for example, polymeric polycarboxylates and polyethylene glycols, normally used in detergents. Nonlimiting examples of the dispersing agents are given in WO-A-95/19951. Protonated amines, such as those described in WO-A-93/25648, and terephthalate/alkylene oxide copolymers, such as those described in WO-A-96/21715 can be used to enhance dispersion stability.
  • Optical Brighteners Any known brightener used in detergents can be used. Suitable brighteners include, but are not limited to, derivatives of stilbene, pyrazoline, coumarin, and carboxylic acid. Nonlimiting examples of suitable brighteners are given in WO-A-95/19951 and WO-A-96/21715.
  • Suds Suppressors Any known compound that suppresses or reduces the formation of suds is suitable for use. Such compounds include, but are not limited to, silicones, silica-silicone mixtures, monocarboxylic fatty acids and soluble salts thereof, high molecular weight hydrocarbons such as paraffin, and fatty acid esters of monoalcohols. These and other suitable suds suppressors are described in WO-A-95/19951 and EP-A-0579295.
  • Fabric Softeners Any known fabric softener compound can be used.
  • suitable fabric softener compounds include clay softeners, conventional quaternary ammonium softening agents, anionic softeners, nonionic softeners, and cationic softeners. These and other suitable fabric softeners are described in WO-A-95/04802, WO-A-95/19951 , and WO-A-
  • (k) Detersive Surfactants Various surfactant materials such as anionic, nonionic, cationic, ampholytic, and zwitterionic surfactants can be used.
  • suitable surfactants include linear alkyl sulfonates ("LAS"), C ⁇ -C,,, alkyl benzene sulfonates, primary and secondary branched-chain and random C 10 -C 20 alkyl sulfates ("AS”), and polyhydroxy fatty acid amide surfactants.
  • compositions of the present invention can be formulated with other cationic surfactants which do not correspond to the formula in Claim 1 , especially those described in WO 98/35002.
  • liquid carriers such as, for example, water and C, to C 4 monohydric alcohols, thickening agents, viscosity control agents, di-(higher alkyl) cyclic amines, aqueous emulsions of predominantly linear polydialkyl or alkyaryl siloxanes absorbency enhancers, pH modifiers such as bases and acids, nonionic or other deflocculating agents, hydrotropes, colorants, perfumes, perfume carriers, preservatives, opacifiers, fluorescers, anti-shrinking agents, anti-wrinkle agents, anti-spotting agents, bactericides, germicides, fungicides, anti-corrosion agents, drape imparting agents, antistatic agents, ironing agents, wetting agents, strength additives such as carboxymethyl cellulose and water-soluble cationic polymers.
  • liquid carriers such as, for example, water and C, to C 4 monohydric alcohols, thickening agents, viscosity control agents, di-(higher alkyl) cycl
  • the formulations of the present invention can be in various forms, such as, for example, aqueous or anhydrous liquid formulations, super concentrate liquid formulations, gel formulations, or solid formulations such as granules, powders or tablets. These solid formulations can be obtained by a suitable process known in the art, such as grinding the composition, or depositing it onto solid substrates.
  • the formulations of the present invention which have a pH below 1 1 when diluted for normal use conditions are preferred. It is also preferred that the formulations have a pH above 1.5 when diluted for normal use. Normal use conditions are known in the art.
  • the present invention concerns formulations comprising at least 0.01 , preferably from 0.1 to 40, most preferably from 1 to 15 percent by weight of cationic ester surfactant of the invention.
  • the liquid formulations of the present invention may be prepared by mixing the composition of the invention with a liquid carrier and, optionally, at least one other of the above-mentioned ingredients in a standard formulation mixing equipment and in accordance with techniques known to a person skilled in the art. Low-shear mixing is generally sufficient to adequately and uniformly mix the composition within the formulation. The final formulation, whether in concentrated or diluted form must be easily pourable by the end user.
  • compositions of the present invention Due to the compatibility of compositions of the present invention with conventional detergent ingredients and because they are hydrolytically stable at typical detergent pHs they can conveniently be formulated in detergents, including softergents. Furthermore, the compositions of the present invention, being compatible with softening active ingredients and being hydrolytically stable at typical pHs, can conveniently be formulated with any known softening active ingredients into a fabric softener, especially for the design of clear fabric softening formulations.
  • DMAE 2-(dimethylamino) ethanol
  • 421 g Radiacid TM 626 (2 moles) in a 1 liter reaction flask equipped with a 20 cm by 2.5 cm vigreux column and slowly heated.
  • DMAE is commercially available, but could be formed by reacting dimethyiamine with ethylene oxide, as is known in the art.
  • the Radiacid TM 626 reportedly corresponds to a mixture of fatty acids having typical chain lengths primarily in the range of C 12.14 , but with about 13 percent of the acids having chain lengths in the range of C 6 -C 10 .
  • the reported Iodine values of Radiacid TM 626 was 7 to 11.
  • the temperature was gradually increased to 200°C, continuously distilling off the excess of DMAE and the reaction water at a temperature of 90°C to 100°C, over a period of 12 hours.
  • the mixture was then heated for an hour at 130°C/100 mbar to remove any residual DMAE.
  • the product contained 98 weight percent esters as determined by gas chromatography and was liquid at room temperature.
  • esteramine was then dissolved in acetone (60 percent solution), mixed with a 50 percent molar excess of methylchloride and subsequently quatemized at 95°C for a period of 17 hours. After this the conversion of the esteramine was 100 percent, as determined by free amine titration with perchloric acid. The acetone was evaporated, leaving a sticky product with a melting point greater than 130°C, at which temperature the product started to decompose.
  • acetone 60 percent solution
  • Example 1 The equipment and procedure were as described Example 1.
  • the reaction mixture consisted of 255 g 1-(dimethylamino)-2-propanol (DMAP; 2.45 moles) and 362 g (1.63 moles) Radiacid TM 600.
  • the Radiacid TM 600 reportedly corresponds to a mixture of fatty acids having typical chain lengths primarily in the range of C 12.14 , but with less than 1.53 percent of the acids having chain lengths in the range of C 6 to C 10 .
  • the reported Iodine values of Radiacid TM 600 is 8 to 12.
  • the reaction procedure took 13 hours.
  • the final product contained 98 percent ester and was liquid at room temperature.
  • the esteramine thus formed was then quatemized as an 80 percent solution in isopropanol (IPA) with dimethylsulfate (DMS)(1 :0.9 mole ratio). This exothermic reaction took less than 1 hour at 100°C. The final product was 90 percent quatemized.
  • the melting range was 20°C to 40°C (20 percent IPA); the IPA-free product melted at a temperature greater than 100°C.
  • the esteramine formed in this Example was also quatemized using methylchloride.
  • An 80 percent solution of the esteramine in acetone was reacted with a 50 percent molar excess of methylchloride at 95°C for a period of 16 hours, and resulted in a degree of quatemization was 100 percent.
  • the acetone free product was a sticky solid which decomposed above 130°C.
  • Example 1 or 2 A similar procedure as described under Example 1 or 2 can also be used for esterifying DMAB and then quaternizing the esterified product.
  • KOH as a 55 weight percent solution in water can be dissolved in DMAP at a level of 0.4 weight percent. This mixture can then be placed in a jacketed pressure vessel, equipped with stirrer, and heated to 120°C. Ethylene oxide (EO) in a mole ratio EO:DMAP of 3:1 can then be slowly added. The reaction will be exothermic and the temperature should be controlled by gradual addition of EO. The reaction should be finished within 1 hour after the addition has been completed. Thereafter, the KOH catalyst can be neutralized such as by the addition of acetic acid, or be removed such as by absorption using magnesium silicate and then filtration.
  • EO Ethylene oxide
  • the DMAP-3EO alkanolamine thus formed can then be esterified by heating it with an equimolecular amount of fatty acid at 200°C/20 mbar for a period of approximately 10 hours, while distilling off the water formed during the reaction.
  • Any fatty acid can be used, such as RadiacidTM 409 , and is reported to correspond to a mixture of fatty acids having typical chain lengths primarily in the range of C 16.18 , and Iodine values less than 2.
  • Other fatty acids which may be suitably used, especially for facilitating the formation of clear formulations include oleic acid (such as RadiacidTM 212, or 150), soft tallow (RadiacidTM 441 , or 403), or partially hydrogenated soft tallow (RadiacidTM 406). A conversion of 98 percent can be reached.
  • the DMAP-3EO ester thus formed can be quatemized according the methods mentioned in Examples 1 or 2, such that a 90 percent dimethylsulfate quatemized or 100 percent methylchloride quatemized product can be formed.
  • KOH as a catalyst can be added to DMAE, DMAP, or DMAB, as described in Example 4. This mixture can then be placed in a reaction vessel and heated as described in Example 4. Alkylene oxide can then be added as before, replacing the 3 moles of EO with for example, 3 moles of propylene oxide (PO), 1 mole of PO followed by 2.5 moles of EO, 2 moles of EO followed by 2 moles of PO, or 1 mole of butylene oxide (BO) followed by 2.5 moles of EO.
  • PO propylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • the reactions with more than one alkylene oxide can also be carried out with the simultaneous addition of the different oxides (for example, 2 moles of an EO and 2 moles of PO can be simultaneously fed into the reactor), such that alkanolamines with random alkylene oxide sequences are formed. Furthermore it is possible, as is known in the art, to alternate block and random feeds in the same preparation. As before, the reaction will be exothermic and the temperature should be controlled by gradual addition of alkylene oxide. The reaction should be finished within 1 hour after the addition has been completed. Thereafter, the KOH catalyst can be neutralized with acetic acid.
  • the alkanolamine thus formed can then be esterified by heating it with an equimolecular amount of fatty acid at 200°C/20 mbar for a period of approximately 10 hours, while distilling off the water formed during the reaction, following the procedure set out in Example 4.
  • the formed ester can then be quatemized following the procedure set out in
  • Monoesterquats from Example 1 and Example 2 were tested on their hydrolytic stability by a) monitoring (by titration) the acid formation of a 5 weight percent dispersion in water at 50°C, adjusted to pH 4, for a period of 4 weeks, and b) monitoring (again by titration) the acid formation of a 5 weight percent dispersion in Ariel FuturTM (commercially available liquid formulation produced by Procter & Gamble and purchased in The Netherlands in February 1998), at 35°C, and a pH of approximately 8, for a period of 2 weeks.
  • Ariel FuturTM commercially available liquid formulation produced by Procter & Gamble and purchased in The Netherlands in February 1998)

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Abstract

L'invention concerne une classe de tensioactifs d'ester cationique présentant une stabilité hydrolytique. L'invention concerne, en particulier, des compositions d'ester alcanolaminé quaternisé, ledit ester étant basé sur un alcool secondaire ou tertiaire, et/ou sur l'utilisation d'un ester alcanolaminé alcoxylaté dans un détergent, dans un nettoyant, pour des soins personnels, ou dans des applications pour adoucisseur de tissu.
EP99962973A 1998-12-03 1999-12-02 Tensioactifs d'ester cationique utilises dans des formulations liquides et pulverulentes Withdrawn EP1135362A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11079998P 1998-12-03 1998-12-03
US110799P 1998-12-03
PCT/US1999/028520 WO2000032559A1 (fr) 1998-12-03 1999-12-02 Tensioactifs d'ester cationique utilises dans des formulations liquides et pulverulentes

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EP1135362A1 true EP1135362A1 (fr) 2001-09-26

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EP (1) EP1135362A1 (fr)
AU (1) AU1930400A (fr)
CA (1) CA2352118A1 (fr)
WO (1) WO2000032559A1 (fr)

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Publication number Priority date Publication date Assignee Title
FR2926979B1 (fr) * 2008-02-04 2010-12-17 Oreal Nouveaux composes cationiques, compositions les comprenant, utilisation comme conditionneur, et procede de traitement cosmetique.
WO2010029267A1 (fr) * 2008-09-12 2010-03-18 L'oreal Composition cosmetique comprenant des esters d'ammonium quaternaires et des polymeres epaississants, utilisation pour le conditionnement des cheveux
FR2935899B1 (fr) * 2008-09-12 2010-09-17 Oreal Composition cosmetique comprenant des esters d'ammonium quaternaires et des polymeres epaississants particuliers,a ainsi qu'a leur utilisation pour le conditionnement des cheveux
FR2935900B1 (fr) * 2008-09-12 2010-09-17 Oreal Composition cosmetique comprenant des esters d'ammonium quaternaires et des polymeres epaississants particuliers, utilisation pour le conditionnement des cheveux
TWI778497B (zh) * 2020-01-29 2022-09-21 美商艾德凡斯化學公司 胺基酸界面活性劑
EP4299708A1 (fr) * 2022-06-27 2024-01-03 The Procter & Gamble Company Composition liquide pour le nettoyage de la vaisselle à la main

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GB2040985B (en) * 1977-06-29 1982-10-20 Procter & Gamble Low-phosphate detergent composition for fabric washing
GB8414944D0 (en) * 1984-06-12 1984-07-18 Ici Plc Fabric conditioners
FR2574424B1 (fr) * 1984-12-12 1987-01-16 Interox Procede d'activation du peroxyde d'hydrogene dans des bains de lavage ou de desinfection, compositions solides de lavage et de desinfection et utilisation de telles compositions dans des bains pour le lavage ou la desinfection des textiles
ATE142193T1 (de) * 1991-07-29 1996-09-15 Kao Corp Sa Verfahren zur herstellung von quartären verbindungen
GB9513999D0 (en) * 1995-07-08 1995-09-06 Procter & Gamble Detergent compositions
DE19713852A1 (de) * 1997-04-04 1998-10-08 Henkel Kgaa Aktivatoren für Persauerstoffverbindungen in Wasch- und Reinigungsmitteln
EP0869114A1 (fr) * 1997-04-04 1998-10-07 Dow Europe S.A. Composition assouplissante et procédés pour sa préparation

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Title
See references of WO0032559A1 *

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CA2352118A1 (fr) 2000-06-08
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