WO2000021918A1 - Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation - Google Patents

Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation Download PDF

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Publication number
WO2000021918A1
WO2000021918A1 PCT/US1998/021683 US9821683W WO0021918A1 WO 2000021918 A1 WO2000021918 A1 WO 2000021918A1 US 9821683 W US9821683 W US 9821683W WO 0021918 A1 WO0021918 A1 WO 0021918A1
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Prior art keywords
formulation
structural formula
group
compounds
compound
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PCT/US1998/021683
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English (en)
Inventor
Robert O. Keys
Floyd E. Friedli
Damon M. Dalrymple
Craig Poffenberger
David E. Whittlinger
Wangqi Hou
Monna Manning
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Goldschmidt Chemical Corporation
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Application filed by Goldschmidt Chemical Corporation filed Critical Goldschmidt Chemical Corporation
Priority to EP98949809A priority Critical patent/EP1121341A1/fr
Priority to CA002347036A priority patent/CA2347036A1/fr
Priority to PCT/US1998/021683 priority patent/WO2000021918A1/fr
Priority to KR1020017004698A priority patent/KR20010106516A/ko
Priority to AU96047/98A priority patent/AU9604798A/en
Publication of WO2000021918A1 publication Critical patent/WO2000021918A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds

Definitions

  • the present invention relates to amine and quaternary ammonium compounds and formulations thereof useful as, for instance, fabric softeners, paper debonders, hair conditioners, skin conditioners, paper deinking and ink floatation agents, asphalt emulsion agents, corrosion inhibitor agents, ore floatation agents, pesticide emulsion agents, car drying aid sprays, drilling fluid additives, and the like.
  • fabric softeners paper debonders, hair conditioners, skin conditioners, paper deinking and ink floatation agents, asphalt emulsion agents, corrosion inhibitor agents, ore floatation agents, pesticide emulsion agents, car drying aid sprays, drilling fluid additives, and the like.
  • Conventional quats Conventional quats
  • a variety of conventional quats have been proposed for many uses, for example, in fabric softeners for home use or for industrial and institutional use.
  • fabric softening compounds are generally cationic (positively charged).
  • anionic detergent ingredients and cationic softening ingredients are present in the same aqueous solution, they have a natural tendency to complex together or even precipitate out of solution. This complexation or precipitation reaction interferes with the performance of both the detergent compounds and the softening compounds and is therefore undesirable.
  • Q 2 together may be a -CH 2 CH 2 - group to form a six-membered piperazine ring; or, if R** is a -CH 2 CH 2 - group, Q 3 and Q together may be a -CH 2 CH 2 - group to form a six-membered piperazine ring; m is 0 to 4; r is 0 to 2; each of v, w, x, y, and z is independently 1 to 8; i is 0 to 1 , j is 0 to 1 , and each k is 0 to 1 , and the sum of (i+j +k) is 0 to 4; each A " is independently an anion as defined below; and n is the number of moles of A ⁇ needed to give the compound of structural formula (1) a zero net charge.
  • Another embodiment of the invention comprises compounds of structural formula (1) is compounds wherein at least one of v, w, x, y, and z is greater than 1. In a preferred embodiment of the invention, each of v, w, x, y, and z is greater than 1.
  • Another embodiment of the invention includes compounds of structural formula (1) wherein substituents Q 1 , Q 2 and Q 3 are not present, or there is one or more substituents selected from Q 1 , Q 2 and Q 3 and any such substituent present is -H.
  • Another embodiment of the present invention further comprises an amine salt, polyamine salt, or mixture thereof.
  • compositions useful for instance as fabric softeners, comprising (a) a component selected from the group consisting of compounds of structural formula (1) and mixtures thereof; (b) water; and (c) optionally, one or more solvents or cosolvents.
  • Another aspect of the present invention comprises a composition comprising:
  • a compound of structural formula (1) (a) a compound of structural formula (1); and (b) a second surfactant selected from the group consisting of anionic surfactants, cationic surfactants, zwitterionic surfactants, nonionic surfactants, amphoteric surfactants, and blends thereof.
  • the secondary surfactant is selected from the group consisting of: nonylphenol ethoxylates; C 5 -C 20 linear or branched alcoxylates using EO, PO, iPO, BO, or mixtures thereof; amine ethoxylates; fatty amide ethoxylates; fatty acid ethoxylates; carboxylated nonionics; ⁇ -polyglucosides; and mixtures thereof.
  • the secondary surfactant is an alkanolamide.
  • the secondary surfactant is an amine oxide.
  • a further aspect of the present invention comprises a composition comprising: (a) a compound of structural formula (1); (b) a solvatrope or coupling agent or blends thereof; and (c) an oil or hydrophobic organic component and blends thereof.
  • the composition further comprises water.
  • the amount of the compound of structural formula (1) is about 0J wt. % to about 65 wt. % of the formulation; the amount of solvatrope or coupling agent is about 0J wt. % to about 65 wt. % of the formulation, the amount of oil or hydrophobic organic component is about 0J wt. % to 65 wt. % of the formulation, and the amount of water is about 20 to 99 J wt. % of the formulation, preferably about 35 wt. % to about 99 J wt. % .
  • the iodine value of the fatty acid used to make the compound of structural formula (1) ranges from about 30 to about 140, preferably from about 80 to about 120, most preferably, from about 90 to about 110.
  • the composition is emulsified into a microemulsion.
  • the composition is clear.
  • the amount of the compound of structural formula (1) is about 5 wt. % to about 50 wt. % of the formulation, preferably about 10 wt. % to about 30 wt. % , and most preferably about 15 wt. % to about 25 wt.
  • the amount of solvatrope or coupling agent is about 2 wt. % to about 15 wt. % of the formulation, preferably about 3 wt. % about 10 wt. %, and most preferably about 6 wt. % to about 10 wt. % ;
  • the amount of oil or hydrophobic organic component is about 5 wt. % to 50 wt. % of the formulation, preferably about 10 wt. % to about 30 wt. % , and most preferably about 15 wt. % to about 20 wt. %;
  • the amount of water is about 10 to 70 wt. % of the formulation, preferably about 20 wt. % to about 60 wt. % , and most preferably about 30 wt. % to about 50 wt. % .
  • the composition is used as a personal care formulation, wherein the amount of the compound of structural formula (1) is about 0J wt. % to about 65 wt. % of the formulation, preferably about 0J wt. % to about 25 wt. % , and most preferably about 0J wt. % to about 5 wt. % ; the amount of solvatrope or coupling agent is about 0J wt. % to about 65 wt. % of the formulation, preferably about 0J wt. % about 25 wt. % , and most preferably about 0J wt. % to about 0.5 wt.
  • the composition is a pesticide emulsion agent formulation further comprising water.
  • the composition is a pesticide formulation comprising the pesticide emulsion agent formulation and an effective amount of pesticide.
  • the pesticide formulation comprises an amount of compound of structural formula (1) ranging from about 5 wt. % to about 50 wt. % , preferably from 10 wt. % to about 40 wt. % , of the pesticide formulation.
  • aspects of the instant invention include using the compounds of structural formula (1) either alone or in formulations, as a fabric softener (either alone or in a combination detergent/fabric softener), as a car spray microemulsion, as a paper debonder, as a hair or skin conditioner, as a corrosion inhibitor, as an asphalt emulsifier, as an organoclay ingredient, or as an agricultural product emulsifier.
  • the polyethoxylated compounds of structural formula (1) may also find uses as textile treatments, particularly when used in conjunction with a resin bath.
  • Other aspects of the present invention include such methods and processes using the compounds of structural formula (1) either alone or in formulations.
  • a particularly preferred embodiment of the present invention comprises mixtures of compounds corresponding to structural formula (1), such that degrees of quaternization or protonation (including unquaternized, unprotonated compounds), degrees of ester ification, and chain lengths and molecular weights of different molecules within the mixture will differ such that the respective properties can be represented as an average over all the molecules present in the mixture.
  • properties such as the degree of quaternization can be expressed as average values which may lie between integer whole numbers.
  • the groups depicted as Q 1 , Q 2 and Q 3 represent substituents which, when present, protonate (if they are -H) or quaternize (if they are any other group) the respective nitrogen atoms to which they are bonded. While the structure of structural formula (1) embraces compounds ranging from compounds wherein no nitrogen atom is quaternized or protonated with a corresponding Q substituent, through compounds wherein every nitrogen atom is quaternized or protonated with a Q substituent, one preferred embodiment is compounds wherein the compound of structural formula (1) should be partially quaternized.
  • the term “partially” is meant to convey that at least one nitrogen atom on the molecule as depicted in structural formula (1) does not have a Q substituent attached to it.
  • mixtures of compounds which are diamines that is, in structural formula (1), the subscript r is zero
  • Another preferred embodiment is compounds, and mixtures thereof, in which there are either no Q substituents or the only Q substituents present are -H.
  • Such Q substituents can be present in a degree such that all nitrogen atoms are protonated, or fewer than all nitrogen atoms are protonated ("full” and "partial” protonation, respectively).
  • the compounds of structural formula (1) may also have any of a range of degrees of esterification, depending on the application.
  • the degree of esterification can range from 1 to 4 for diamines, and up to 5 or 6 for- triamines or tetramines, respectively.
  • the preferred degree of esterification that is, the total number of R A groups present, preferably ranges from about 2 to about 4.
  • a preferred degree of esterification is from 1 to about 3 for clear, translucent formulations and about 2 to 3.5 for easily dispersible formulations, and the more preferred degree of esterification is about 2.0 to about 2.5; for triamines and tetramines the preferred degree of esterification should be adjusted accordingly; that is, approximately one additional ester group per additional amine group.
  • the compound of structural formula (1) is prepared having only about 1 to about 2 ester groups per molecule to ensure that the molecule as a whole is less hydrophobic than those that would typically be employed in other applications.
  • the respective R C(O)- acyl groups can all have the same chain lengths. More preferably they have several chain lengths and degrees of carbon-carbon unsaturation, reflecting the fact that the fatty acyl groups can be derived from naturally occurring sources which contain mixtures of fatty acids with differing chain lengths and differing degrees of carbon-carbon unsaturation. Examples of such sources include fatty acids derived from the following sources: tallow, fish oils, canola (including fatty acids derived from partially hydrogenated canola), jojoba, palm, coconut, avocado, wheat germ, rapeseed, olive, orange, corn, linseed, neem, peanut, safflower, sesame seed, soybean, sunflower seed, and cocoa butter.
  • sources include fatty acids derived from the following sources: tallow, fish oils, canola (including fatty acids derived from partially hydrogenated canola), jojoba, palm, coconut, avocado, wheat germ, rapeseed, olive, orange, corn, lin
  • Preferred materials are tallow, canola, and palm.
  • a clear formulation the use of an unsaturated fatty acid is preferred to make the compound of structural formula (1) or at least a portion of the compound of structural formula (1) used in the formulation.
  • the degree of unsaturation of a compound is typically expressed as the iodine value (I.V.).
  • the IN. of the fatty acid used to make the compound of structural formula (1) ranges from about 30 to about 140, more preferably the IN. ranges from about 80 to about 120, most preferably the IN. ranges from about 90 to about 110.
  • Such clear formulations have an additional advantage: they generally exhibit excellent freeze/thaw recovery.
  • a 1"5 can each, independently, be ethyl, propyl (straight or branched) or butyl (straight or branched).
  • each of the A 1"5 groups present is the same, for ease of synthesis. It is also preferred that each of A 1"5 is ethyl or propyl (especially isopropyl). Further preferred embodiments of compounds of structural formula (1) are described herein with respect to the various formulation capabilities of the products of this invention.
  • R* is a -CH 2 CH 2 - group
  • Q 1 and Q 3 together or Q 1 and Q 2 together may be a -CH 2 CH 2 - group to form a six-membered piperazine ring
  • R** is a -CH 2 CH 2 - group
  • Q and Q together may be a -CH 2 CH 2 - group to form a six-membered piperazine ring.
  • the present invention also provides compounds and formulations that are useful in personal care products such as hair or skin conditioners.
  • the present invention provides formulations that impart softness, lubricity, and improve the surface appearance of the skin or hair.
  • the hair conditioners additionally reduce the tendency for tangling, improve the manageability, and impart a soft feel to the hair strands.
  • Such hair conditioners are applied as dilute emulsions to the hair following its wash or may be incorporated into a combined conditioner and shampoo composition, also known as a conditioning shampoo, two-in-one shampoo, or two-in-one.
  • Such hair and skin conditioning formulations typically incorporate effective amounts, for example, 0J wt. % to 10 wt.
  • emollients emollients, humectants, and/or slip and conditioning agents, such as organopolysiloxanes and the like, to create formulations that are monophasic and can be made to be translucent or even clear.
  • slip and conditioning agents such as organopolysiloxanes and the like
  • compositions of the present invention are particularly useful in applications that take advantage of their ability to disperse hydrophobic material, to stabilize foam, and to enhance the penetration and wetting exhibited by the compositions. Examples of such compositions and applications are set forth below, each revealing an additional aspect of the present invention.
  • the compounds and formulations of the present invention may be used as oil dispersants and oil slick dispersant formulations for application onto oil, for example, onto a film of oil, to disperse the oil.
  • the compounds and formulations of the present invention may also be used as oil well stimulation and oil recovery aids for injection into oil wells in order to penetrate into the surface of the borehole and assist liberation of crude oil from the matrix material into the borehole, from which it can be brought to the surface.
  • the compounds and formulations of the present invention may be used as vehicles for hydrophobic sheeting agents such as mineral oil and silicone oil.
  • hydrophobic sheeting agents such as mineral oil and silicone oil.
  • oils can readily be dispersed in compositions, according to the present invention, and the resulting formulations are highly satisfactory when sprayed or otherwise applied to a surface, such as a freshly washed automobile surface, to impart a lustrous, water-repellent film to the surface.
  • the compounds and formulations of the present invention may also be used as rinse aids, such as used in automatic dishwashers, wherein application of the composition of the present invention disperses residual hydrophobic matter, including cleaner residues and films.
  • the compounds and formulations of the present invention may be used as paper deinking and ink flotation agents for treating waste inked paper by addition to the pulp slurry such that the ink is liberated from the paper and prevented from redepositing onto the paper.
  • the ink is typically dispersed or even fully solubilized in the resulting solution when the ink particles are floated from the fibers.
  • the compounds and formulations of the present invention may also be used as asphalt emulsion agents for emulsifying finely divided asphalt (at loadings of typically 1-20 wt. %), with or without particulate filler such as sand, in an aqueous phase which comprises the composition according to the present invention.
  • the compounds and formulations of the present invention may be used as suspension concentrates and emulsifiable concentrates of herbicides, pesticides, miticides, fungicides, or bactericides, wherein one or more liquid or solid, generally hydrophobic, active ingredients are dispersed in a composition according to the present invention.
  • the resulting concentrate can be applied as a concentrate on or around desired vegetation, but is more often mixed with water (for example, at the point of use) to form a final dilute formulation having the desired concentration of active ingredient(s) .
  • This application takes advantage of the noteworthy property of this invention that addition of the water does not disrupt the monophasic state, nor the fluidity, of the formulation.
  • HMD A hexamethylenediamine
  • BHMT bis(hexamethylene)triamine
  • MPMD 2- methylpentamethylenediamine
  • the alkoxylating agents may be ethylene oxide (EO), propylene oxide (PO), isopropylene oxide (iPO), or butylene oxide (BO), or (less preferred) a mixture thereof, depending on the desired choice of alkyl groups to become attached to the respective nitrogen atoms.
  • EO ethylene oxide
  • PO propylene oxide
  • iPO isopropylene oxide
  • BO butylene oxide
  • the number of moles of alkylene oxide reactant and the reaction conditions are established such that the terminal primary amine hydrogen atoms are disubstituted with hydroxyalkyl, and each of the secondary amines, if any, is monosubstituted with hydroxyalkyl.
  • polyethoxylated polyamine products typically are quite dark (4-8 Gardner units) after only 8 to 12 moles of EO are added.
  • the alkoxylated product is esterified by reaction of fatty acids with the respective hydroxyl groups resulting from the alkoxylation.
  • the molecule may be completely esterified, but it is preferred for formulation reasons to achieve only partial esterification. There should, however, be at least one ester group per molecule of structural formula (1).
  • the esterification is carried out with carboxylic acids of structural formula R ⁇ C(0)OH, wherein R A is straight or branched alkyl or alkenyl containing 9 to 21 carbon atoms and 0 to 4 carbon-carbon double bonds.
  • esterification can be carried out with an appropriate quantity of one such carboxylic acid, it is preferred for reasons of economy, product performance, and convenience to employ mixtures of carboxylic acids each corresponding to structural formula R C(0)OH.
  • carboxylic acids each corresponding to structural formula R C(0)OH.
  • mixtures of such fatty acids from various animal and vegetable origins are conveniently commercially available.
  • One example of such material is tallow fatty acids which, as is generally known in this field, is a mixture of fatty acids predominantly composed of fatty acids containing 14, 16, and 18 carbon atoms, and 0, 1 , and 2 degrees of unsaturation.
  • Other preferred sources include coconut fatty acids and canola fatty acids, although any suitable fatty acid may be used.
  • Esterification is carried out under conventional conditions, well-known to the chemist in this field, allowing for the withdrawal of byproduct water.
  • the number of moles of fatty acid is selected to provide the desired average degree of esterification in the mixture of products formed upon esterification.
  • the esterified product or mixture of esterified products is quaternized and/or protonated.
  • the esterified product can be completely quaternized, but it is preferred to carry out partial quaternization only, if any.
  • Quaternization is carried out under conditions well known in this field for quaternization of amines, by reaction of the esterified amine with a suitable quaternizing agent.
  • the quaternizing agents have the formulas Q A and Q " A, which can of course be the same and preferably are the same. With triamines and tetramines a second (or third) quaternizing agent Q 3 A can be used; it is likewise preferably the same as Q'A and Q 2 A.
  • Protonation can be carried out by reacting the esterified product or mixture of products with an acid of the formula HA, such as hydrochloric acid, or other strong acids, such as sulfuric acid or phosphoric acid.
  • an acid of the formula HA such as hydrochloric acid, or other strong acids, such as sulfuric acid or phosphoric acid.
  • Each of the foregoing reactions can be carried out in solvent or in solvent-free conditions, in each case employing conditions well established for the respective reactions in this field.
  • Preferred diamine compounds of the present invention include hexamethylenediamine (HMD A) alkoxylated ester diamines or quats, most preferably HMD A alkoxylated ester quats, which are made according to the above method. Accordingly, HMD A may be reacted with 4 moles of alkoxylating agent per mole of HMD A. If a polyalkoxylated HMD A ester compound is desired, more than 4 moles of alkoxylating agent would be used, for example, 4J to 32 moles of ethylene oxide. The resulting HMD A alkoxylate is then esterified by reaction with 1 to 4 moles of fatty acid, for example, tallow fatty acid.
  • HMD A hexamethylenediamine
  • HMD A alkoxylated ester may then be quaternized with up to 2 moles of dimethyl sulfate (DMS) per mole of HMD A.
  • DMS dimethyl sulfate
  • Example 1 below details the synthesis of a particular HMD A monoalkoxylated ester quat.
  • Preferred triamine compounds of the present invention include bis(hexamethylene)triamine (BHMT) alkoxylated ester quats, most preferably BHMT ethoxylated ester quats, which are made according to the above method. Accordingly, BHMT may be reacted with 5 moles of ethylene oxide per mole of BHMT.
  • BHMT bis(hexamethylene)triamine
  • a polyalkoxylated BHMT ester compound is desired, more than 5 moles of alkoxylating agent would be used, for example, 5J to 40 moles of ethylene oxide.
  • the resulting BHMT alkoxylate is then esterified by reaction with 5 moles of fatty acid, for example, canola fatty acid.
  • the resulting BHMT alkoxylated ester may then be quaternized with up to 3 moles of dimethyl sulfate (DMS) per mole of BHMT.
  • DMS dimethyl sulfate
  • the products as described herein exhibit a number of desirable properties making them particularly suitable for formulation into commercial products such as fabric softeners and other commercial products, as mentioned above.
  • the compounds of structural formula (1) can readily be formulated into useful compositions such as aqueous compositions, which achieve the desired functionality and which are clear, that is, transparent or translucent. This property can be realized at a variety of concentrations of active ingredient, with or even without special solvents or coupling agents.
  • microemulsion formulations can be made that improve the ease of application and effectiveness of the resulting formulation.
  • Emulsion or microemulsion formulations according to the present invention have many applications, for example, as car “cheater” wax spray technology to improve beading and act as a drying aid, as fabric softeners, and as personal care products, for example, as a moisturizer/conditioner if the compound of structural formula (1) is not skin irritating.
  • emulsions or microemulsions may find uses in paper debonding/finishing, as emulsifiers for silicone oils and pesticides, and as emulsifiers/softeners for textile finishing.
  • Such formulations include three components: (a) compound of structural formula (1), (b) a solvatrope or coupling agent and blends thereof, and (c) an oil or hydrophobic organic component and blends thereof, which are blended in water.
  • These microemulsion formulations give stable, clear (translucent) products that do not go through thick or viscous gel phases but disperse readily and quickly into very fine particle size microemulsions when diluted or dispersed in water.
  • These microemulsions have many additional advantages over conventional microemulsions, such as the products sold by Witco Corporation under the tradename CARSPRAYTM: reduced particle size, improved beading and sheeting over, and improved biodegradability, especially when used with methyl ester oils.
  • the amount of the compound of structural formula (1) is about 0J wt. % to about 65 wt. % of the formulation, preferably about 0J wt. % to about 25 wt. % , and most preferably about 0J wt. % to about 5 wt. % ;
  • the amount of solvatrope or coupling agent is about 0J wt. % to about 65 wt. % of the formulation, preferably about 0J wt. % about 25 wt. % , and most preferably about 0J wt. % to about 0.5 wt.
  • the amount of oil or hydrophobic organic component is about 0J wt. % to 65 wt. % of the formulation, preferably about 0J wt. % to about 25 wt. % , and most preferably about 0J wt. % to about 5 wt. % ; and the amount of water is about 20 to 99.7 wt. % of the formulation, preferably about 35 wt. % to about 99.7 wt. % , and most preferably about 65 wt. % to about 99.7 wt. % .
  • Example 29 A further example of personal care microemulsions according to the invention is provided below as Example 29.
  • the amount of the compound of structural formula (1) is n about 5 wt. % to about 50 wt. % of the formulation, preferably about 10 wt. % to about 30 wt. % , and most preferably about 15 wt. % to about 25 wt. % ;
  • the amount of solvatrope or coupling agent is about 2 wt. % to about 15 wt. % of the formulation, preferably about 3 wt. % about 10 wt. % , and most preferably about 6 wt. % to about 10 wt. % ;
  • the amount of oil or hydrophobic organic component is about 5 wt.
  • % to 50 wt. % of the formulation preferably about 10 wt. % to about 30 wt. % , and most preferably about 15 wt. % to about 20 wt. % ; and the amount of water is about 10 to 70 wt. % of the formulation, preferably about 20 wt. % to about 60 wt. % , and most preferably about 30 wt. % to about 50 wt. % .
  • the products are biodegradable.
  • the embodiments which have no Q substituents, or wherein the only Q substituents are -H exhibit particularly high biodegradability.
  • the compounds of structural formula (1) exhibit advantageous stability, solubility, and freedom from excessively objectionable color and odor.
  • the color and odor stability is exhibited in formulations wherein the compound or compounds of structural formula (1) are the only nitrogenous compounds present.
  • Color and order stability is also exhibited in formulations wherein one or more compounds of structural formula (1) is present with one or more additional conventional quaternary ammonium compounds.
  • the compounds of the present invention improve the color and odor stability of the other conventional quaternary ammonium compounds present.
  • the color stability property is shown in the following data, in which color stability was assessed by heating samples of each product shown in Table I to 110°C in open tubes in an air circulation oven, periodically measuring the color in Gardner units and calculating the color change over time:
  • the compounds of structural formula (1) have many potential uses, in particular, they exhibit highly satisfactory fabric softening capabilities.
  • the compounds of structural formula (1), as well as mixtures of such compounds can be advantageously formulated appropriately into products useable as fabric softeners.
  • the pH of the formulation as a whole should be below 5, and preferably 2.5 to 4.0, in order to maintain low susceptibility of the ester functionality to hydrolysis in water.
  • the preferred method for providing or adjusting the desired pH value is adding small amounts of an acid, such as HCl or H 2 S0 4 , consistent with appropriate adjustment of the average degree of esterification and average degree of quaternization mixture of compounds corresponding to structural formula (1).
  • Preferred emulsions useful as fabric softener compositions can contain about 2 wt. % to about 80 wt. % , preferably 5 wt. % to 30 wt. % , and more preferably 6 wt. % to 25 wt. % , of one or more compounds corresponding to structural formula (1).
  • higher solids contents can be provided more easily with lower degrees of quaternization.
  • higher degrees of quaternization such as a degree of quaternization approaching 2.0 for a diamine
  • the compounds of structural formula (1) can be formulated into compositions, including clear fabric softener compositions.
  • Such fabric softening composition would typically include water and one or more of the solvents which are conventionally used in formulating fabric softeners.
  • solvents include ethanol, isopropanol, hexylene glycol, propylene glycol, diethylene glycol, or similar solvent of mixture thereof, as a concentrate or more dilute form, depending on the application. Selection of a suitable solvent for a particular application is well-known to those of skill in the art.
  • Such formulations generally comprise about 10 wt. % up to about 50 wt. % of one compound of structural formula (1) or a mixture thereof.
  • the compounds of structural formula (1) can be formulated with greater ease than is encountered with conventional quaternary ammonium fabric softener actives.
  • compositions including compounds of structural formula (1) can be prepared at active concentrations of 40 wt. % or higher, for example, even 50 wt. % or higher.
  • the preparation itself of such formulations is much simpler: the freedom from gelation means that when a formulator chooses to manufacture a more concentrated product for resale to the consumer, there is no need for special treatment to deal with gel formation.
  • the freedom from gel formation means that the consumer can use the more concentrated product directly without concern that a gelled byproduct would form.
  • the consumer could add a concentrated fabric softener composition according to the present invention directly into the wash water in the wash or rinse cycle, without any apprehension that a gel will form that that would reduce softening efficiency or leave a deposit on the clothes.
  • Additional conventional quaternary ammonium compounds or salts may be present with the compound or compounds of structural formula (1) in accordance with the present invention.
  • the compounds presented below are only examples of conventional quaternary compounds that are suitable for use in the formulations of the present invention.
  • these conventional quaternary ammonium compounds may have an anion to provide electrical neutrality and, in general, such anion may be any anion which is not deleterious to the properties of the overall compound.
  • the counteranion may be selected, without limitation, from the group consisting of fluoride, chloride, bromide, iodide, chlorite, chlorate, hydroxide, hypophosphite, phosphite, phosphate, carbonate, formate, acetate, lactate, and other carboxylates, oxalate, methyl sulfate, ethyl sulfate, benzoate, and salicylate, and the like.
  • Preferred examples of the anions are chloride, bromide, methyl sulfate, ethyl sulfate, and salicylate.
  • a ⁇ represents the anion group, if the anion is divalent (has a charge of -2), A " represents half of the anion group, if the anion is trivalent (has a charge of -3), A ⁇ represents a third of the anion group, and so on.
  • the conventional quats that may be formulated with the compounds of structural formula (1) in accordance with the present invention include, but are not limited to, nitrogenous compounds selected from the group consisting of quaternized or acid salt derivatives of: (i) alkylenediamines, including compounds of the formula:
  • each Ri is an acyclic alkyl or alkylene C 12 -C 21 hydrocarbon group, each Z is -(R O) 0 . 4 H, or -R 2 H, and R 2 and R 3 are divalent C C 6 alkylene groups; (ii) substituted imidazoline compounds having the formula:
  • reaction products of higher fatty acids with alkylenetriamines in, for example, a molecular ratio of about 2: 1 , the reaction products containing compounds of the formula:
  • G is -O- or -NH- and R, and R 2 are defined as above; and mixtures thereof.
  • Preferred examples of compounds of structural formula (i) are those derived from hydrogenated tallow fatty acids and the hydroxyalkylalkylenediamine is N-2- hydroxyethylethylenediamine, such that Rj is an aliphatic C 15 -C 21 hydrocarbon group, and R 2 and R 3 are divalent ethylene groups.
  • a preferred example of a compound of structural formula (iii) is stearic hydroxyethyl imidazoline, wherein R[ is an aliphatic C 21 hydrocarbon group and R 2 is a divalent ethylene group.
  • a preferred example of compounds of structural formula (iii) is N,N'-ditallowalkanoyldiethylenetriamine where R ⁇ is an aliphatic C 15 -C 21 hydrocarbon group and R 2 and R 3 are divalent ethylene groups.
  • a preferred example of compounds of structural formula (iv) is l-tallowamidoethyl-2-tallowimidazoline wherein R, is an aliphatic C 15 -C 21 hydrocarbon group and R 2 is a divalent ethylene group.
  • Both N,N"- ditallowalkanoyldiethylenetriamine and l-tallowethylamido-2-tallowimidazoline are reaction products of tallow fatty acids and diethylenetriamine, and are precursors of the cationic fabric softening agent methyl- l-tallowamidoethyl-2-tallowimidazolinium methylsulfate.
  • N,N'- ditallowalkanoyldiethylenetriamine and l-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco Co ⁇ oration.
  • Methyl- l-tallowamidoethyl-2-tallowimidazolinium methylsulfate is available from Witco Co ⁇ oration under the tradename VARISOFT® 475.
  • Suitable quats are those containing one long chain acyclic aliphatic C 8 - C 22 hydrocarbon group, selected from the group consisting of: (v) acyclic quaternary ammonium salts having the formula:
  • R 4 - ⁇ - R 5 e wherein R 4 is an acyclic aliphatic C 8 -C 22 hydrocarbon group, alkyl, benzyl or (C 4 -
  • R 5 and R ⁇ are C,-C 4 saturated alkyl or hydroxyalkyl groups, and A " is an anion as defined above;
  • substituted imidazolinium salts having the formula: wherein Rj is an acyclic alkyl or alkylene C 12 -C 21 hydrocarbon group, R 7 is hydrogen or a C r C 4 saturated alkyl or hydroxyalkyl group, and A " is an anion as defined above;
  • substituted imidazolinium salts having the formula: wherein Rj is an acyclic alkyl or alkylene C 12 -C 21 hydrocarbon group, R 7 is hydrogen or a C r C 4 saturated alkyl or hydroxyalkyl group, and A " is an anion as defined above;
  • substituted imidazolinium salts having the formula:
  • R 4 is an acyclic aliphatic C 8 -C 22 hydrocarbon group and A " is an anion as defined above; and (ix) alkanamide alkylene pyridinium salts having the formula:
  • Ri is an acyclic aliphatic C 12 -C 21 hydrocarbon group
  • R 2 is a divalent C r C 6 alkylene group
  • a "" is an anion as defined above; and mixtures thereof.
  • Examples of compounds of structural formula (v) are the monoalkyltrimethylammonium salts such as monotallowtrimethylammonium chloride, mono(hydrogenated tallow)-trimethylammonium chloride, palmityltrimethylammonium chloride and soyatrimethylammonium chloride, available from Witco Co ⁇ oration under the tradenames ADOGEN® 471 , ADOGEN® 441 , ADOGEN® 444, and ADOGEN® 415, respectively.
  • R 4 is an acyclic aliphatic C 16 -C 18 hydrocarbon group
  • R 5 and R 6 are methyl groups.
  • Mono(hydrogenated tallow)trimethylammonium chloride and monotallowtrimethylammonium chloride are preferred.
  • R 4 is a C 22 hydrocarbon group, which is available from the Humko Chemical Division of Witco Co ⁇ oration under the tradename KEMAMINE® Q2803-C; soyadimethylethylammonium ethylsulfate wherein R 4 is a C 16 -C ⁇ 8 hydrocarbon group, R 5 is a methyl group, R 6 is an ethyl group, and A " is an ethylsulfate anion; and methyl bis(2-hydroxyethyl)octadecylammonium chloride wherein R 4 is a C 18 hydrocarbon group, R 5 is a 2-hydroxy ethyl group and R 6 is a methyl group.
  • An example of a compound of structural formula (vii) is 1 -ethyl- 1-(2- hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfate wherein Rj is a C 17 hydrocarbon group, R 2 is an ethylene group, R 5 is an ethyl group, and A is an ethylsulfate anion.
  • Other quats useful in the present invention include cationic nitrogenous salts having two or more long chain acyclic aliphatic C 8 -C 22 hydrocarbon groups or one long chain acyclic aliphatic C 8 -C 22 hydrocarbon group and an arylalkyl group. Examples include: (x) acyclic quaternary ammonium salts having the formula:
  • R4 wherein each R 4 is an acyclic aliphatic C 8 -C 22 hydrocarbon group, R 5 is a C r C 4 saturated alkyl or hydroxyalkyl group, R 8 is selected from the group consisting of R 4 and R 5 groups, and A ⁇ is an anion as defined above; (xi) diamido quaternary ammonium salts having the formula:
  • each Rj is an acyclic alkyl or alkylene C 12 -C 21 hydrocarbon group
  • each R 2 is a divalent alkylene group having 1 to 3 carbon atoms
  • R 5 and R 9 are C r C 4 saturated alkyl or hydroxyalkyl groups
  • a " is an anion as defined above
  • R 4 is an acyclic aliphatic C 8 -C 22 hydrocarbon carbon group, each R 5 is a C r C saturated alkyl or hydroxyalkyl group, and A " is an anion as defined above;
  • each Rj is an acyclic aliphatic C 12 -C 21 hydrocarbon group
  • R 2 is a divalent alkylene group having 1 to 3 carbon atoms
  • R 5 and A " are as defined above, or R 5 is -H
  • ester-substituted imidazolinium salts having the formula:
  • R 1 ? R 2 , R 5 , and A " are as defined above; and mixtures thereof.
  • Examples of compounds of structural formula (x) are the well-known dialkyldimethylammonium salts such as ditallowdimethylammonium chloride, ditallowdimethylammonium methylsulfate, di(hydrogenated tallow)dimethylammonium chloride, distearyldimethylammonium chloride, dibehenyldimethylammonium chloride. Di(hydrogenated tallow)dimethylammonium chloride and ditallowdimethylammonium chloride are preferred.
  • dialkyldimethylammonium salts examples include di(hydrogenated tallow)dimethylammonium chloride (available from Witco Co ⁇ oration under the tradename ADOGEN® 442); ditallowdimethylammonium chloride (available from Witco Co ⁇ oration under the tradename ADOGEN® 470); distearyldimethylammonium chloride (available from Witco Co ⁇ oration under the tradename AROSURF® TA-100); dicocodimethyl ammonium chloride (available from Witco Co ⁇ oration under the tradename ADOGEN® 462), and dibehenyldimethylammonium chloride, wherein R 4 is an acyclic aliphatic C 22 hydrocarbon group (available from the Humko Chemical Division of Witco Co ⁇ oration under the tradename KEM AMINE® Q-2802C).
  • Examples of compounds of structural formula (xi) are methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate, wherein Ri is an acyclic aliphatic C 15 -C 17 hydrocarbon group, R 2 is an ethylene group, R 5 is a methyl group, R 9 is a hydroxyalkyl group and A " is a methylsulfate anion; both of these materials are available from Witco Co ⁇ oration under the tradenames VARISOFT® 222 and VARISOFT® 110, respectively.
  • An example of a compound of structural formula (xiii) is dimethylstearylbenzylammonium chloride, wherein R 4 is an acyclic aliphatic C 18 hydrocarbon group, R 5 is a methyl group and A " is chloride, which is available from Witco Co ⁇ oration under the tradename VARISOFT® SDC.
  • Examples of compounds of structural formula (xiv) are 1 -methyl- l-tallowamidoethyl-2-tallowimidazolinium methylsulfate and 1 -methyl- 1- (hydrogenated tallowamidoethyl)-2-(hydrogenated tallow)imidazolinium methylsulfate wherein Ri is an acyclic aliphatic C 15 -C 17 hydrocarbon group, R 2 is an ethylene group, R 5 is a methyl group and A " is a chloride anion; available from Witco Co ⁇ oration under the tradenames VARISOFT® 475 and VARISOFT® 445, respectively.
  • R n is selected from the group consisting of: (a) -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 OH, or straight chain aliphatic hydrocarbon groups each of which contains from 12 through 24 carbon atoms, (b) ether groups each of which has the structure: R 13 0(CH 2 0) y -, (c) amide groups each of which has the structure :
  • R 12 is a straight chain aliphatic hydrocarbon group containing from 8 to 32 carbon atoms
  • R 13 is a straight chain aliphatic hydrocarbon group containing from 8 to 21 carbon atoms
  • R !4 is a straight chain aliphatic hydrocarbon group containing from 7 to 17 carbon atoms
  • Z is an alkoxy group containing one oxygen atom and either two or three carbon atoms
  • A is an anion as defined above
  • m is an integer from 1 through 12
  • y is an integer which is either 2 or 3.
  • Yet additional examples of fabric softening compounds useful in the present invention include: (xvii) compounds having the formula:
  • R, 5 is hydrogen or C C 4 alkyl, i 5
  • each R 16 is C r C 4 alkyl or ( Ri 8 )y each R 17 is a C 8 -C 28 alkyl or alkenyl group, R 18 is hydrogen or C r C 4 alkyl, each y is 0 or 1, x is 0 or 1 , and each n is from 1 to 6;
  • R 19 and R 20 are selected independently from the group consisting of C 1-22 alk(en)yl aryl or alkyl aryl groups
  • R 2 j is hydrogen or a C 1-22 alk(en)yl, aryl or alkyl-aryl group or is 0-R 22
  • R 22 is a C 1-22 alk(en)yl, aryl or alkyl-aryl group
  • R 21 and R 22 optionally contain 1 to 10 alkylene oxide units or functional groups selected from hydroxy, amine, amide, ester, and ether groups; the aryl groups being possibly derived from 1 heterocyclic compounds
  • at least one of the R 19 and R 20 groups contains 10 or more carbon atoms; and where the sum of carbon atoms in R ⁇ 9 + R 20 + R 2 ⁇ is equal to or greater than 14.
  • the sum of carbon atoms in R 19 +R 20 is equal to or greater than 16.
  • compounds of structural formula (xviii) include N,N-ditallow acetamide, N,N-dicoconut acetamide, N,N-dioctadecyl propanamide, N-dodecyl-N-octadecyl acetamide, N-hexadecyl-N- dodecyl butanamide, N,N-ditallow benzamide, NN-dicoconut benzamide, and N,N-ditallow 2-phenyl acetamide.
  • Additional fabric softening compounds useful in the present invention include all ester quaternaries, including but not limited to: (xix) compounds of the following structural formulas:
  • each R 2 ⁇ is independently a saturated or unsaturated alkyl or alkylene radical containing 12 to 22 carbon atoms; each Q is independently an alkyl group containing 1 to 4 carbon atoms, benzyl, -CH 2 CH 2 OH, -CH 2 CH(OH)CH 3 , or R 21 -C(0)-(0-(Alk 21 )) 1 . 4 -; each Alk 21 is independently C 2 H 4 , C 3 H 6 or C 4 H 8 ; and A " is an anion as defined above; (xx) compounds of the formula:
  • each A , 2 * 2 is the same or different and each is alkyl containing up to 3 carbon atoms, benzyl, or H-(Alk 22 -0) 1-3 -Alk 22 - wherein each Alk 22 represents -CH 2 CH(CH 3 )-,
  • a 22 can be hydrogen;
  • D is methyl, ethyl, propyl, -(CH 2 ) 1-3 COO-, benzyl or hydrogen;
  • i is 0 or 1 and j is 0 or 1 , provided that the sum of (i + j) is 1 or 2;
  • each X " is a straight or branched saturated or unsaturated aliphatic group containing up to 3 carbon-carbon double bonds and containing 11 to 23 carbon atoms;
  • n is two minus the number of -(CH 2 ) 1-3 COO- substituents present; and
  • a ⁇ is an anion as defined above;
  • R 23 -[C(0)0(CH 2 ) 1-5 ]o- ⁇ -C(0)NH(CH 2 ) 2 . 5 -N(R 23a )(R 23b )-(CH 2 ) 2 . 5 -OC(0)R 23 A- wherein each R 23 is independently straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms; R 23a is straight or branched alkyl or hydroxyalkyl containing 1 to 3 carbon atoms, benzyl, or -C 2 H 4 OC(0)R 26 , wherein R 26 is straight or branched alkyl or alkenyl containing 8 to 22 carbon atoms; R 23b is -H, -CH 3 , -C 2 H 5 or benzyl; and A ⁇ is an anion as defined above; and (xxii) compounds of the following structural formulas:
  • Preferred examples of compounds of structural formulas (xxii) include methyl diethanolamine (MDEA) ester quats, triethanolamine (TEA) ester quats, for example, di-(tallow carboxy ethyl) hydroxy ethyl methylammonium methosulfate, available from Witco Co ⁇ oration under the tradename REWOQUATTM WE 16, or epichlorohydrin-based ester quats, all of which are used and accepted as fabric softeners worldwide because of their favorable biodegradation profiles, but usually lack the optimum softening performance of other quats.
  • MDEA diethanolamine
  • TAA triethanolamine
  • fabric softener formulations and other formulations which may be clear (translucent or transparent) and easily dispersed in water can be provided by including an appropriate amount of one or more straight or branched alkyl diols containing 4 to 12 carbon atoms, and/or alkoxylates of such diols with up to 40 alkoxy units per diol moiety, wherein the alkoxylate chains are composed of alkoxy units which are ethoxy, propoxy or butoxy or mixtures thereof, and preferably ethoxy or isopropoxy.
  • diol and diol alkoxylate hydrotropes or coupling agents are added to the formulations to increase the amount of the relatively water-insoluble surfactants that can be solubilized into the system. In most cases, they do not act as surfactants to lower surface tension but they often allow surfactants in the presence of salts or electrolytes to be added and subsequently dispersed into water at higher concentrations or at lower viscosities of the formulation than is otherwise achieved using only surfactant and water.
  • These coupling agents assist surfactants by increasing the surfactant's solubility in water and its stability in the formulation, especially in the presence of salts, electrolytes and/or pH agents.
  • each X and each Y is ethylene (that is, -C 2 H 4 -), propylene (that is, -C 3 H 6 -), or butylene (that is, -C 4 H 8 -);
  • x is 0-40;
  • y is 0-40; the sum (x+y) is 0-40; and
  • R ⁇ is straight, branched or cyclic alkyl containing 4 to 12 carbon atoms.
  • R ⁇ contains 7-12 or even 7-9 carbon atoms.
  • the alkylene residue R ⁇ in structural formula (T) represents a saturated, straight-chain, branched-chain, or cyclic moiety containing 4 to 12 carbon atoms. It is preferred that R is branched, wherein the term "branched" is intended to encompass structures having one side alkyl chain, more than one side alkyl chain, or one or more side alkyl chains, one or more of which is itself branched. Branched structures include cyclic structures substituted with one or more alkyl groups, the alkyl groups being straight or branched.
  • R groups include such groups as -CH 2 C(CH 3 ) 2 CH 2 -, -CH 2 CH(CH 2 CH 2 CH 2 CH 3 )-, -CH 2 C(CH 3 ) 2 CH(CH(CH 3 ) 2 )-, -CH 2 CH 2 CH 2 -, -C(CH 3 ) 2 CH 2 -, -(CH 2 ) 6 -, -CH 2 CH(CH 3 )CH 2 -,-CH 2 CH(CH 2 CH 3 )CH 2 CH 2 CH 2 CH 2 -, and
  • each poly(alkoxy) chain can be up to 40 but it is preferred that each chain contains 1 to 10 repeating alkoxy units or more preferably 1 to 5 alkoxy units.
  • the preferred alkoxy chains are poly (ethoxy), or are composed of 1 to 2 ethoxy units capped with a chain of 1 to 5 propoxy units.
  • Compounds of structural formula (T) defined above are in many instances commercially available. Compounds of structural formula (T) can be prepared in straightforward manner familiar to those of ordinary skill in this art by obtaining or preparing the corresponding
  • o precursor diol of structural formula HO-R -OH o precursor diol of structural formula HO-R -OH, and then alkoxylating the precursor diol with a stoichiometrically appropriate number of moles of the desired corresponding alkylene oxide, such as ethylene oxide, propylene oxide, and/or butylene oxide.
  • the alkoxylation will preferentially occur at only one of the hydroxyl groups, particularly where one of them is a primary hydroxyl and the other is a secondary hydroxyl.
  • the hydroxyl group at which alkoxylation is desired not to occur can be protected by preliminarily reacting it with a suitable protecting group such as a lower alkyl moiety or an esterifying substituent. Thereafter, following the alkoxylation, the protecting group is removed in a known manner.
  • Preferred examples of compounds of the foregoing structural formula (T) include any one, or mixtures, of 2J,4-trimethyl-l J-pentanediol (TMPD) and/or 2- ethylhexane-l J-diol, and/or the reaction product of TMPD and/or 2-ethylhexane-l J-diol with 1 to 10 moles of ethylene oxide, and preferably with 1 to 5 moles of ethylene oxide, as well as analogs alkoxylated with other C 3 or C 4 alkyl oxides or mixtures of any of C 2 , C 3 and/or C 4 alkyl oxides.
  • TMPD 2J,4-trimethyl-l J-pentanediol
  • 2- ethylhexane-l J-diol 2- ethylhexane-l J-diol
  • compositions which contain one or more compounds of structural formula (1) can also contain one or a mixture of compounds of structural formula (E)
  • R F2 F containing 1 to 10 carbon atoms, and R is substituted with 0 to 3 hydroxyl groups, and R can optionally be substituted with a group of the structure -OC(0)-R wherein R is straight, cyclic or branched alkyl containing 1 to 15 carbon atoms and is optionally substituted with a hydroxyl group.
  • Preferred compounds of structural formula (E) include
  • R contains 2 or 3 carbon atoms, for example, glycol and glyceryl derivative, or R E2 contains about 8 carbon atoms, for example, derivatives of 2J,4-trimethylpentanediol or of 2-ethylhexanediol.
  • Preferred compounds of structural formula (E) include 2,2,4- trimethyl-lJ-pentanediol monoisobutyrate, hydroxypivalyl hydroxypivalate, and the monoester of TMPD with hydroxypivalic acid.
  • Formulations can also contain what may be termed aesthetic additives to provide properties such as fragrance, preservative, viscosity control, and color. Such additives are discussed below.
  • the formulations according to the present invention generally exhibit highly satisfactory viscosities, generally as pourable and even sprayable fluids.
  • suitable non-quaternary compound surfactants may be used in combination with the compounds and formulations of the invention, depending on the application.
  • suitable anionic surfactants may include, without limitation, the alkylbenzene sulfonates, ⁇ -olefin sulfonates, and xylene sulfonates available from Witco Co ⁇ oration under the WITCONATE® trademark. While these surfactants may be unsuitable for personal care applications because they may cause skin and eye irritation, surfactants suitable for personal care applications may be used in other non-personal care applications.
  • suitable anionic surfactants would include, without limitation, ammonium lauryl sulfate, sodium lauryl sulfate, any ⁇ -olefin sulfonate, ammonium laureth sulfate (2 or 3 moles), sodium laureth sulfate (2 or 3 moles), sodium myristyl sulfate, sodium myristeth sulfate (1-4 moles), ammonium xylene sulfonate, sodium xylene sulfonate, TEA dodecylbenzene sulfonate, TEA lauryl sulfate, ammonium pareth sulfate, sodium pareth sulfate, sodium oleth sulfate, derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof.
  • amphoteric surfactants or non-ionic surfactants include betaines, sulfosuccinates, mono- and diglycerides, glycinates, sugars and derivatives thereof, hydroxysultaines, mono- and diacetates, ethoxy lated derivatives of any of the forgoing, and similar compounds known to those of skill in the art, and mixtures thereof.
  • Other surfactants that may be added to these systems include, but are not limited to, alkanolamides, many of which are available from Witco Co ⁇ oration under the WITC AMIDE® tradename.
  • various amine oxides may be used in these systems.
  • Emollients and emulsifiers are also typically used in personal care formulations in combination with the polyester amine compounds and polyquaternary compounds of the invention, depending on the application.
  • the preferred embodiment of this invention may also be used in emulsions that can be used as skin or hair conditioners which can take the form of lotions, creams, leave-on products, and rinse-off products.
  • These systems may also include additional products that may improve the feel and conditioning, or the emolliency of skin and hair.
  • additives and adjuvants can be optionally added to the compounds and formulations of the present invention for their known pu ⁇ oses.
  • additives and adjuvants include, but are not limited to, perfumes, preservatives including bacteriocides and fungicides, insect and moth repelling agents, polymeric soil release agents, antistatic agents, dyes and colorants, especially bluing agents, viscosity control agents, antioxidants, silicones, defoaming agents, antifoaming agents, emulsifiers, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, aloe, humectants, skin protectants, feel modifiers, waxes, glycerine, vitamins and extracts, and mixtures thereof.
  • additives and adjuvants used would depend on the application of the formulation and its desired properties.
  • the additives and adjuvants are well-known to those of skill in the art and the additives and adjuvants listed below are not meant to be an exhaustive list but merely a guide to the types of additives that would typically be used.
  • perfumes or fragrance materials may be added to the compositions and formulations of the present invention.
  • the selection of the perfume or perfumes is based upon the application, the desired effect on the consumer, and preferences of the formulator.
  • Such perfume is preferably present at a level of from about 0.01 % to about 5% , preferably from about 0.05 % to about 3 % , more preferably from about 0.1 % to about 2% , by weight of the total composition.
  • the perfume is composed of fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols having molecular weights from about 90 to about 240; aliphatic ketones having molecular weights from about 150 to about 260; aromatic ketones having molecular weights from about 150 to about 270; aromatic and aliphatic lactones having molecular weights from about 130 to about 290; aliphatic aldehydes having molecular weights from about 140 to about 200; aromatic aldehydes having molecular weights from about 90 to about 230; aliphatic and aromatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320; and mixtures thereof.
  • fragrance materials selected from the group consisting of aromatic and aliphatic esters having molecular weights from about 130 to about 250; aliphatic and aromatic alcohols
  • solubilized, water-soluble preservatives can be added to the present invention.
  • Preservatives are especially preferred when organic compounds that are subject to microorganisms are added to the compositions of the present invention, especially when they are used in aqueous compositions. When such compounds are present, long term and even short term storage stability of the compositions and formulations becomes an important issue since contamination by certain microorganisms with subsequent microbial growth often results in an unsightly and/or malodorous solution.
  • a solubilized water-soluble, antimicrobial preservative which is effective for inhibiting and/or regulating microbial growth in order to increase storage stability of the preferably clear and often aqueous compositions and formulations of the present invention.
  • a broad spectrum preservative for example, one that is effective on both bacteria and fungi.
  • a limited spectrum preservative for example, one that is only effective on a single group of microorganisms, for example, fungi, can be used in combination with a broad spectrum preservative or other limited spectrum preservatives with complimentary and/or supplementary activity.
  • Antimicrobial preservatives useful in the present invention can be biocidal or biostatic compounds.
  • an "effective amount” means a level sufficient to prevent spoilage or prevent growth of inadvertently added microorganisms for a specific period of time.
  • Preferred levels of preservative are from about 0.0001 % to about 0.5 % , more preferably from about 0.0002% to about 0.2% , most preferably from about 0.0003 % to about 0.1 % , by weight of the composition.
  • Bacteriostatic effects can sometimes be obtained for aqueous compositions by adjusting the composition pH to an acid pH, for example, less than about pH 4, preferably less than about pH 3.
  • aqueous compositions of the present invention should have a pH greater than about 3.0, preferably greater than about 4.0, more preferably greater than about 4.5.
  • the preservative can be used at a level which provides an antimicrobial effect on the treated fabrics.
  • composition of the present invention can optionally contain an effective amount of antistatic agent to provide the treated clothes with in-wear static.
  • Preferred antistatic agents are those that are water soluble in at least effective amount, such that the composition remains a clear solution.
  • An example of these antistatic agents is ethyl
  • 3i bis(polyethoxyethanol) alkylammonium ethylsulfate available from Witco Co ⁇ oration under the tradename VARIQUAT® 66. It is preferred that a no foaming, or low foaming, agent is used, to avoid foam formation during fabric treatment. It is also preferred that polyethoxylated agents such as polyethylene glycol or VARIQUAT® 66 are not used when ⁇ -cyclodextrin is used. When an antistatic agent is used it is typically present at a level of from about 0.05% to about 10% , preferably from about 0J % to about 5 %, more preferably from about 0.3% to about 3 % , by weight of the composition.
  • Colorants and dyes, especially bluing agents, can be optionally added to the compositions of the present invention for visual appeal and performance impression. When colorants are used, they are used at extremely low levels to avoid fabric staining. Preferred colorants for use in the present compositions are highly water-soluble dyes, for example,
  • composition of the present invention can optionally contain an effective amount of insect or moth repelling agents.
  • Typical insect and moth repelling agents are pheromones, such as anti-aggregation pheromones, and other natural and/or synthetic ingredients. When an insect and/or moth repellent is used it is typically present at a level of from about 0.005 wt. % to about 3 wt. % of the composition. 6. Polymeric Soil Release Agents
  • Soil release agents are especially desirable additives at levels of from about 0.05 wt. % to about 5 wt. % , preferably from about 0J wt. % to about 4 wt. % , more preferably from about 0J wt. % to about 3 wt. % .
  • Suitable soil release agents are disclosed in U.S. Patent Nos. 4,702,857; 4,711 ,730; 4,713, 194; 4,877,896; 4,956,447; and 4,749,596.
  • polymeric soil release agents comprising block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol.
  • the polymeric soil release agents useful in the present invention can include anionic and cationic polymeric soil release agents. Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Patent No. 4,018,569. Other suitable polymers are disclosed in U.S. Patent No. 4,808,086. Suitable cationic soil release polymers are described in U.S. Patent No. 4,956,447. 7. Viscosity Control Agents
  • Viscosity control agents can be organic or inorganic in nature and may either lower or raise the viscosity of the formulation.
  • organic viscosity modifiers lowering
  • aryl carboxylates and sulfonates for example, benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example, benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example, benzoate, 2-hydroxybenzoate, 2-aminobenzoate, benzenesulfonate, 2-hydroxybenzenesulfonate, 2-aminobenzenesulfonate, etc.
  • fatty acids and esters for example
  • Suitable salts are the halides and acetates of ammonium ion and the group IA and IIA metals of the Periodic Table of the Elements.
  • the amount of ionizable salts used depends on the amount of active ingredients used in the compositions and can be adjusted according to the desire of the formulator. Typical levels of salts used to control the composition viscosity are from 0 to about 10 wt. % , preferably from about 0.01 wt. % to about 6 wt. % , and most preferably from about 0.02 wt. % to about 3 wt. % of the composition.
  • Viscosity modifiers raising or thickening agents can be added to increase the ability of the compositions to stably suspend water-insoluble articles, for example, perfume microcapsules.
  • These viscosity raisers are typically used at levels from about 0.5 wt. % to about 30 wt. % , preferably from about 1 wt. % to about 5 wt. % , more preferably from about 1.5 wt. % to about 3.5 wt. % , and most preferably from about 2 wt. % to about 3 wt. %, of the composition.
  • pearlizing or opacifying agents examples include, but are not restricted to, glycol distearate, propylene glycol distearate, and glycol stearate. Some of these products are available from Witco Co ⁇ oration under the KEMESTER® tradename.
  • vitamins and extracts are often used in the formulations thereof.
  • antioxidants examples include propyl gallate, available from Eastman Chemical Products, Inc. under the tradenames TENOX® PG and TENOX® S-l , and dibutylated hydroxy toluene, available from UOP Inc. under the tradename SUSTANE® BHT.
  • compositions can contain silicones to provide additional benefits, for example, in a fabric application they may provide ease of ironing and improved fabric absorbency.
  • silicones comprises cationic and amphoteric silicones, polysiloxanes, and polysiloxanes having hydrogen-bonding functional groups consisting of amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, amide, ester, and thiol groups.
  • Such polysiloxanes include, but are not limited to, polyether-modified polysiloxanes, amino-modified polysiloxanes, epoxy-modified polysiloxanes, polyhydrido- modified polysiloxanes, phenol-derivative-modified polysiloxanes, ABA-type polysiloxanes, [AB] N -type polysiloxanes, amino [AB] N -type polysiloxanes, including those available from OSi Specialties, Inc. (a division of Witco Co ⁇ oration), under the SILWET®, NUWET®, NUDRYTM, NUSOFTTM, MAGNASOFT® tradenames.
  • Suitable silicones may include polydimethylsiloxanes of viscosity of from about 100 centistokes (cs) to about 100,000 cs, preferably from about 200 cs to about 60,000 cs and/or silicone gums. These silicones can be used in emulsified form, which can be conveniently obtained directly from the suppliers. Examples of these preemulsified silicones are the 60% emulsion of polydimethylsiloxane (350 cs) sold by Dow Corning Co ⁇ oration under the tradename DOW CORNING® 1157 Fluid and the 50% emulsion of polydimethylsiloxane (10,000 cs) sold by General Electric Company under the tradename GENERAL ELECTRIC® SM 2140 silicones. The optional silicone component can be used in an amount of from about 0J wt. % to about 6 wt. % of the composition.
  • Silicone foam suppressants can also be used. These are usually not emulsified and typically have viscosities of from about 100 cs to about 10,000 cs, preferably from about 200 cs to about 5,000 cs. Very low levels are used, typically from about 0.01 % to about 1 % , preferably from about 0.02% to about 0.5 % .
  • Another preferred foam suppressant is a silicone/silicate mixture, for example, Dow Coming's ANTIFOAMTM A.
  • the pH (10% solution) of the compositions of this invention is generally adjusted to be in the range of from about 2 to about 7, preferably from about 2.4 to about 6.5, more preferably from about 2.6 to about 4. Adjustment of pH is normally carried out by including a small quantity of free acid in the formulation. Because no strong pH buffers are present, only small amounts of acid are required. Any acidic material can be used; its selection can be made by anyone skilled in the softener arts on the basis of cost, availability, safety, etc. Among the acids that can be used are methyl sulfonic, hydrochloric, sulfuric, phosphoric, citric, maleic, and succinic. For the pu ⁇ oses of this invention, pH is measured by a glass electrode in a 10% solution in water of the softening composition in comparison with a standard calomel reference electrode. 12. Lubrication and Slip Additives
  • compositions and formulations of the present invention can contain additives such as water, insoluble organics such as fatty acids, fatty esters, triglycerides, oils, alcohols,
  • compositions and formulations of the present invention can contain ethoxylated amines, amphoterics, betaines, polymers such as polyvinylpyrrolidone, and other ingredients that inhibit dye transfer.
  • Paper and tissue softening or debonding compositions of the present invention would typically contain other chemicals commonly used in papermaking or tissuemaking, or to the paper or tissue furnish so long as they do not significantly and adversely affect the softening, absorbency of the fibrous material, and softness enhancing actions of the amine and quaternary ammonium softening compounds of the present invention.
  • the present invention may contain as an optional ingredient from about 0.005 % to about 3.0% , more preferably from about 0.03 % to 1.0% by weight, on a dry fiber basis of a wetting agent.
  • wetting agents may be selected from polyhydroxy compounds, nonionic surfactants such as alkoxylated compounds and linear alkoxylated alcohols.
  • water soluble polyhydroxy compounds that can be used as wetting agents in the present invention include glycerol, polyglycerols having a weight-average molecular weight of from about 150 to about 800, and polyoxy ethylene glycols and polyoxypropylene glycols having a weight-average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000, most preferably from about 200 to about 600.
  • Polyoxy ethylene glycols having an weight-average molecular weight of from about 200 to about 600 are especially preferred. Mixtures of the above-described polyhydroxy compounds may also be used.
  • a particularly preferred polyhydroxy compound is polyoxyethylene glycol having an weight average molecular weight of about 400, available from Union Carbide Co ⁇ oration under the tradename PEG-400.
  • Suitable nonionic surfactants can be used as wetting agents in the present invention. These include addition products of alkoxylating agents such as ethylene oxide (EO), propylene oxide (PO), isopropylene oxide (iPO), or butylene oxide (BO), or a mixture thereof, with fatty alcohols, fatty acids, fatty amines, etc. Any of the alkoxylated materials of the particular type described hereinafter can be used as the nonionic surfactant. Suitable compounds are substantially water-soluble surfactants of the general formula:
  • R 10 for both solid and liquid compositions is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups; primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, preferably from about 10 to about 18 carbon atoms. More preferably the hydrocarbyl chain length for liquid compositions is from about 16 to about 18 carbon atoms and for solid compositions from about 10 to about 14 carbon atoms.
  • Y is typically -0-, -C(0)0-, -C(0)N(R n )-, or -C(0)N(R tile)R ⁇ r , in which R 10 , and R ⁇ , when present, have the meanings given hereinbefore, and/or R n can be hydrogen, and z is at least about 8, preferably at least about 10-11. Performance and, usually, stability of the softener composition decrease when fewer ethoxylate groups are present.
  • nonionic surfactants according to the above formula follow, wherein the integer in parenthesis identifies the number of EO groups in the molecule.
  • the deco-, under-, dodder-, terraced-, and pentadecaethoxylates of n-hexadecanol and ft-octadecanol are useful wetting agents in the context of this invention.
  • Exemplary ethoxylated primary alcohols useful herein as the viscosity/dispersibility modifiers of the compositions are «-octadecanol EO(10); and n-decanol EO(l l).
  • the ethoxylates of mixed natural or synthetic alcohols in the "oleyl" chain length range are also useful herein. Specific examples of such materials include oleyl alcohol EO(l l), oleyl alcohol EO(18), and oleyl alcohol EO(25).
  • oleyl alcohol EO(l l) oleyl alcohol EO(18), and oleyl alcohol EO(25).
  • deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadecaethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol can be used as wetting agents in the present invention.
  • the hexa- through octadecaethoxylates of alkylated phenols, particularly monohydric alkylphenols are useful as the viscosity/dispersibility modifiers of the instant compositions.
  • the hexa- through octadeca-ethoxylates of /?-tridecylphenol, m- pentadecylphenol, and the like are useful herein.
  • Exemplary ethoxylated alkylphenols useful as the wetting agents of the mixtures herein are: /?-tridecylphenol EO(l l) and p- pentadecylphenol EO(18).
  • a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms.
  • alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immediately hereinabove can be ethoxylated and used as wetting agents in the present invention.
  • branched-chain primary and secondary alcohols usually synthesized using the well-known Oxo Process, can be ethoxylated and can be used as wetting agents in the present invention.
  • nonionic surfactant encompasses mixed nonionic surface active agents.
  • the level of surfactant, if used, is preferably from about 0.01 % to about 2.0% by weight, based on the dry fiber weight of the tissue paper.
  • the surfactants preferably have alkyl chains with eight or more carbon atoms.
  • Exemplary anionic surfactants are linear alkyl sulfonates and alkylbenzene sulfonates.
  • Exemplary nonionic surfactants are alkylglycosides including alkylglycoside esters, alkylglycoside ethers, and alky lpoly ethoxylated esters.
  • the present invention may contain as an optional component from about 0.01 wt. % to about 3.0 wt. % , more preferably from about 0J wt. % to about 1.5 wt. % , on a dry fiber weight basis, of a water-soluble strength additive resin.
  • water-soluble strength additive resins may include dry strength additives, permanent wet strength resins, temporary wet strength resins, or a compatible mixture thereof.
  • the term "permanent wet strength resin” refers to a resin which allows the paper sheet, when placed in an aqueous medium, to keep a majority of its initial wet strength for a period of time greater than at least two minutes.
  • Permanent wet strength resins useful herein can be of several types. Generally, those resins which have previously found and which will hereafter find utility in the papermaking art are useful herein. Numerous examples are described by Westfelt in Cellulose Chemistry and Technology, Volume 13, at pages 813-825 (1979). Usually, the wet strength resins are water-soluble, cationic materials. That is to say, the resins are water-soluble at the time they are added to the papermaking furnish.
  • SANTO-RESTM such as SANTO-RESTM 31.
  • Other water- soluble cationic resins useful herein are the polyacrylamide resins.
  • Other types of water- soluble resins useful in the present invention include acrylic emulsions and anionic styrene- butadiene latexes.
  • Still other water-soluble cationic resins finding utility in this invention are the urea formaldehyde and melamine formaldehyde resins. These poly functional, reactive polymers have molecular weights on the order of a few thousand.
  • the more common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • polyethylenimine-type resins find utility in the present invention. More complete descriptions of the aforementioned water- soluble resins, including their manufacture, can be found in TAPPI Monograph Series No. 29, Wet Strength In Paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York: 1965).
  • the above-mentioned permanent wet strength additives are those that produce paper products with permanent wet strength, that is, paper which when placed in an aqueous medium retains a substantial portion of its initial wet strength over time.
  • permanent wet strength in some types of paper products can be an unnecessary and undesirable property.
  • Paper products such as toilet tissues, etc. , are generally disposed of after brief periods of use into septic systems and the like. Clogging of these systems can result if the paper product permanently retains its hydrolysis-resistant strength properties.
  • manufacturers use temporary wet strength additives to paper products for which wet strength is sufficient for the intended use, but which then decays upon soaking in water. Decay of the wet strength facilitates flow of the paper product through septic systems.
  • suitable temporary wet strength resins include modified starch temporary wet strength agents, such as that available from the National Starch and Chemical Co ⁇ oration under the tradename NATIONAL STARCHTM 78-0080. This type of wet strength agent can be made by reacting dimethoxyethyl-N-methyl-chloroacetamide with cationic starch polymers. Modified starch temporary wet strength agents are also described in U.S. Patent ⁇ os. 4,675,394 and 4,981,557. C. Other Additives Other suitable additives may be used in paper and tissuemaking applications, depending on the application. For example, glycerin may also be used in the composition and formulations thereof.
  • the amount of glycerin in the aqueous softening composition can be from about 0J wt. % to about 98 wt. % , more preferably from about 60 to about 80 wt. % , and still more preferably from about 40 to about 60 wt. % , of the composition.
  • the compositions and formulations of the instant invention can contain glycols, such as propylene glycol or polyethylene glycol, instead of or in addition to glycerin in such formulations.
  • humectants include lactic acid and its salts, sugars, ethoxylated glycerin, ethoxylated lanolin, corn syrup, hydrolyzed starch hydrolysate, urea, and sorbitol.
  • Suitable skin protectants include allantoin, kaolin, and zinc oxide.
  • Suitable feel modifiers include corn starch, oat flour, talc, boron nitride, and cyclodextrin.
  • This example illustrates formulations of compounds according to structural formula (1) in conventional solvent systems.
  • a product was made by thoroughly blending the quaternary and solvent, then blending in the fragrance and then the water.
  • the components and the amounts thereof were:
  • the resulting formulations had a cloud point of 45°C, a melting point above 10°C, and a Gardner color of above 0.5.
  • the quaternary product of Run 1-B exhibits little or no gelation upon addition to water.
  • the above formulation was repeated except using a 50:50 (wt.) mixture of products prepared in accordance with Runs 1-A and 1-B.
  • the resulting formulation has a cloud point of 50-55°C and exhibits satisfactory properties.
  • This example illustrates that clear formulations can be made which contain a conventional quaternary ammonium fabric softener compound together with one or a mixture of compounds of structural formula (1) as defined herein.
  • This discovery is particularly unexpected in that many conventional quaternary ammonium fabric softener actives, such as the di(C 8 -C 22 alkyl/alkenyl) di(C r C 4 alkyl) quaternary ammonium compounds, like the one employed in this example, cannot readily be formulated into a clear composition in an acceptable amount using existing solvent systems or solvent/coupling agent systems.
  • Example 3 The composition of Example 3 was made using the procedure used in Example 2. The components and the amounts thereof were:
  • Example 4 Additional formulations employing another solvent system include Example 4 and Example 5, both made by the procedure disclosed in Example 2.
  • exemplary formulation guidelines for fabric softener compositions which include polyester polyquaternary compounds conforming to structural formula (1) include Examples 6 and 7.
  • the use of an unsaturated fatty acid is preferred to make the compound of structural formula (1) or at least a portion of the compound of structural formula (1) used in the formulation.
  • the IN. of the fatty acid used to make the compound of structural formula (1) ranges from about 30 to about 140. more preferably the IN. ranges from about 80 to about 120, most preferably the IN. ranges from about 90 to about 110.
  • fatty acids examples may be derived from the following fats and oils: tallow, fish oils, canola (including fatty acids derived from partially hydrogenated canola), palm, wheat germ, rapeseed, olive, corn, neem, peanut, safflower, sesame seed, soybean, sunflower seed, and cocoa butter.
  • the compounds of structural formula (1) may be used either alone or in combination with other compounds.
  • Such compounds may include conventional quats such as those set forth herein above (see E. ADDITIONAL QUATERNARY AMMONIUM COMPOUNDS).
  • these formulations provide advantageous formulations providing and synergistic or unexpected properties.
  • detergent compounds are generally anionic surfactants and naturally tend to complex with or even precipitate out of solution when cationic softening ingredients are present in the same aqueous solution. This complexation or precipitation reaction interferes with the performance of both the detergent compounds and the softening compounds and is therefore undesirable.
  • Detergents and softeners are therefore generally not added simultaneously in laundry operations to avoid this undesirable complexation or precipitation reaction; however, as North American washing machines typically rinse the clothes only once before fabric softener is added to the washload, even if the fabric softener is added during a rinse cycle (as is typically done), residual anionic detergent compounds present in the fabric complexes with the cationic softener compounds, often rendering about 15% to 30% or more of the softener inactive. It has been found that certain conventional quats, particularly the ester quats of structural formula (xxii), in combination with compounds of structural formula (1) provide an advantageous fabric softening formulation with su ⁇ rising resistance to complexation with anionic surfactants.
  • formulations of compounds according to the present invention that are formulated into a microemulsion.
  • such formulations generally include three components: (a) compound of structural formula (1), (b) a solvatrope or coupling agent and blends thereof, and (c) an oil or hydrophobic organic component and blends thereof, which are blended in water.
  • Suitable solvatropes or coupling agents may be selected from the diols and alkoxy lates corresponding to structural formulas (T) or (E), TMPD, TMPD alkoxylates, ethanol, isopropanol, butanol, 1 J-cyclohexanedimethanol (1,2- CHDM), 1 ,4-cyclohexanedimethanol (1 ,4-CHDM), HPHP glycol, isopentyldiol, 1 ,2- hexanediol, ethylene glycol butyl ether, hexylene glycol, 2-butoxy ethanol (sold by Union Carbide under the tradename butyl CELLOSOLVE®), C 6 -C 12 diols/triols and ester diols/triols, glycol ethers, and the like.
  • Oils and hydrophobic organic components may be selected from the fatty C 8 -C 22 methyl esters, such as methyl oleate, mineral seal oils, silicone oils, fatty acids, monoglycerides, diglycerides, triglycerides, dialkyl esters, and the like, depending on the application.
  • the methyl esters are the preferred oil based on performance and biodegradability, although mineral seal oil is preferred in car drying aid applications.
  • An example of such a microemulsion is the following formulation.
  • HMDA is ethoxylated using 4 moles of ethylene oxide per mole of HMDA.
  • the resulting HMDA ethoxylate is esterified with 1.5 to 2 moles of tallow fatty acid per mole of HMDA and the resulting HMDA ethoxylated ester is quaternized with 2 moles of DMS.
  • the HMDA ethoxylated ester quat therefore contains only 1.5 to 2 ester groups per HMDA molecule.
  • This HMDA compound is therefore less hydrophobic than many of the other examples of compounds according to structural formula (1) given in other Examples for other applications.
  • this compound is useful as an emulsifier for organic compounds, for example, when formulated with pesticides, other surfactants and dispersants, and water, the resulting formulation would make a useful agricultural pesticide spray, the HMDA ethoxylated ester quat encouraging the organic components to remain dispersed in the water, allowing efficient transfer and coverage in treating plants.
  • Examples 16 to 18 provide farther examples of this use of the compounds of structural formula (1) and formulations thereof.
  • the polyquaternary compound is prepared having only about 1 to about 2 ester groups per molecule to ensure that the molecule as a whole is less hydrophobic than those that would typically be used in other applications.
  • This example illustrates formulations of compounds according to structural formula (1) for use as a herbicide emulsion agent.
  • a compound according to structural formula (1) for example, HMDA + 12 moles EO + I J moles canola fatty acid, or mixture thereof is added to a solvent or solvent mixture and water and a herbicide is inco ⁇ orated therein and an emulsion formed.
  • the amount of the polyquaternary compound is generally from about 5 wt. % to about 50 wt. % , preferably from about 10 wt. % to about 40 wt. % , most preferably from about 15 wt. % to about 30 wt. % , of the herbicide concentrate composition.
  • a typical formulation might be:
  • Example 17 illustrates formulations of compounds according to structural formula (1) for use as a pesticide emulsion agent formulation.
  • Example 17 does not inco ⁇ orate the pesticide itself, instead an appropriate amount of pesticide must be added to the pesticide emulsion agent formulation to make a pesticide emulsion concentrate, which is diluted with water by the user and applied in the dilute form.
  • an appropriate amount of pesticide must be added to the pesticide emulsion agent formulation to make a pesticide emulsion concentrate, which is diluted with water by the user and applied in the dilute form.
  • 10-30 wt. % of the pesticide emulsion agent formulation is used to in the pesticide emulsion concentrate, that is, there is 70-90 wt. % pesticide in the pesticide emulsion concentrate, which is the form it will generally be commercialized.
  • the final customer will then dilute the pesticide emulsion concentrate (pesticide/emulsifier package) into water for actual application of pesticide.
  • a compound according to structural formula (1) for example, BHMT + 15 moles EO + I J moles canola fatty acid, or mixture thereof is added to a solvent or solvent mixture and water and a pesticide is inco ⁇ orated therein and an emulsion formed.
  • the amount of the polyquaternary compound is generally from about 20 wt. % to about 70 wt. %, preferably from about 15 wt. % to about 50 wt. %, most preferably from about 20 wt. % to about 40 wt. % , of the pesticide emulsion agent composition.
  • a typical emulsion agent formulation might be:
  • the compounds of structural formula (1) may also be used as an asphalt emulsifier as an additive for asphalt.
  • the compound of structural formula (1) is prepared having only about 1 to about 2 ester groups per molecule to ensure that the molecule as a whole is less hydrophobic than those that would typically be employed in other applications.
  • the possible applications in asphalt products are as a cationic rapid set (CRS) emulsion for chip seal, as a cationic medium set (CMS) for mixing grade applications, in a slurry seal or microsurfacing application, or in a roofing and driveway sealer.
  • CRS cationic rapid set
  • CMS cationic medium set
  • the amount of the compound of structural formula (1) in such an application would likely include from about 0J5 wt. % to about 2.0 wt. % , preferably about 0J0 wt. % to about 0J5 wt. % , and most preferably about 0J5 wt.
  • the fatty amine should be protonated in order to dissolve in the water.
  • the pH of the emulsifier solution should be less than about 6.5, and may be adjusted with any strong acid to have a pH of between about 1.0 and about 5.0, preferably between about 2.0 to about 4.0, most preferably between about 2.0 and about 3.0.
  • the possible applications in asphalt products are as a cationic slow set emulsion, cationic quick set emulsion, tack coat, fog seal, base stabilization, prime coat, slurry seal, microsurfacing, industrial asphalt emulsion, or filled asphalt emulsion.
  • the amount of the compound of structural formula (1) in such an application would likely include from about 0J wt. % to about 8.0 wt. % , preferably about 0J0 wt. % to about 5.0 wt. % , and most preferably about 0.5 wt. % to about 2.0 wt. % , of the asphalt.
  • the fatty amine should be protonated in order to dissolve in the water.
  • the pH of the emulsifier solution should be less than about 7.0, and may be adjusted with any strong acid to have a pH of between about 1.0 and about 5.0, preferably between about 2.0 to about 4.0, most preferably between about 2.0 and about 3.0.
  • This example illustrates formulations of compounds according to structural formula (1) for use in corrosion inhibition, for example, for lubricating oil or oil field use.
  • a compound according to structural formula (1) for example, HMDA + 4 moles EO + 2 moles canola fatty acid, or mixture thereof is added to lubricating or other oils as a corrosion inhibitor.
  • the polyamine may be used alone or in combination with a surfactant and/or coupling agent, which may be inco ⁇ orated with the polyamine in a formulation or applied separately. When used, an effective amount is applied to the oil or oil mixture that will come in contact with the metal.
  • the term "effective amount” denotes the amount of polyamine compound that would be effective to inhibit corrosion.
  • the amount of the polyamine compound ranges from about 0.001 wt. % to about 5 wt. % , preferably from about 0.01 wt. % to about 1 wt. % , most preferably from about 0.01 wt. % to about 0.5 wt. % , of the oil mixture in which it is used.
  • This example illustrates formulations of compounds according to structural formula (1) for use in a lubricant and anti-balling agent for silicate muds and other water- based muds, for example, to lubricate drill strings to prevent stuck pipe, bit-balling, or string balling associated with drilling wells.
  • the apparatus for drilling and general lubrication processes in well-known to those of skill in the art, and are disclosed, for example, in U.S. Patent Nos. 5,586,608; 5,593,954; and 5,639,715.
  • a compound according to structural formula (1) for example, BHMT + 5 moles EO + 2.5 moles canola fatty acid, or mixture thereof is added to lubricating or other oils effective to inhibit stuck pipe, bit balling, or string balling.
  • the polyamine may be used alone or in combination with a surfactant and/or coupling agent, for example, propylene glycols or ethoxylated glycols,
  • an effective amount of polyamine is applied to the lubricant mixture as used in the drilling operation.
  • the term "effective amount” denotes the amount of polyamine compound that would be effective to inhibit stuck pipe, bit balling, or string balling.
  • the amount of the polyamine compound ranges from about 0.001 wt. % to about 5 wt. % , preferably from about 0.01 wt. % to about 2 wt. % , most preferably from about 0.05 wt. % to about 0.5 wt. %, of the lubricating mixture in which it is used. If used in a formulation, a typical formulation might be:
  • This example illustrates formulations of compounds according to structural formula (1) for use as a mineral and coal dewatering agent, for example, for removal of water by means of a filtration dewatering apparatus known to those of skill in the art.
  • a compound according to structural formula (1) for example, HMDA + 4 moles EO + 3 moles tallow fatty acid + 2 moles DMS, or mixture thereof is added to the mineral slurry prior to mechanical dewatering, the process becoming more effective as a result.
  • the amount of the polyquaternary compound is generally from about 20 wt. % to about 95 wt. % , preferably from about 30 wt. % to about 80 wt. % , most preferably from about 50 wt. % to about 75 wt. % , of the dewatering agent formulation.
  • a typical formulation might be:
  • Examples 22 to 24 are specific examples, while Example 24 presents a general softener/debonder formulation according to the present invention.
  • Example 22 was a thick liquid while Examples 23 and 24 were both clear liquids; all of Examples 22 to 24 were easy to disperse in water.
  • the softener/debonder formulation of the present invention would include the components set forth in Example 25 in the amounts shown.
  • a dispersion of the appropriate formulation was prepared in water at 25-30°C.
  • An aqueous slurry of SW fibers was treated with the dispersion of the respective formulation at dosages corresponding to 1 , 3, and 5 lb. (#) debonder/ton of fiber.
  • Tissue weight handsheets approximately 60 g/m , were prepared according TAPPI procedure T-205.
  • the handsheets were equilibrated under conditions specified in TAPPI Method T-402.
  • the handsheets were tested for tensile and so ⁇ tive rate and capacity according to TAPPI Methods T-492 and T-561 , respectively.
  • the results are presented in Table II. In each case the softness of the product treated with Examples 22 to 24 was better than the product treated with a comparable amount of AROSURF® PA-801 debonder.
  • HMDA ester quats are effective debonders and compare favorably in performance to an industry standard. Indeed, the HMDA ester quats afford debonded tissue products with good absorbency rates and capacities and hand panels confirm that the formulations of the instant invention give better softness than AROSURF® PA-801 debonder. In addition, the HMDA ester quat formulations have low odor and each of the above formulations was easy to disperse in warm water. As with all of the Examples given, Examples 22 to 25 are only exemplary and, although applied here to softwood fibers, may be used with hardwood fiber, recycled fiber, baggasse fibers, fluff pulp, and all natural papermaking fibers and blends thereof.
  • EXAMPLE 26 This example illustrates formulations of compounds according lo structural formula (1) for use as deinking agents, for example, in recycled paper products. Generally such formulations are added to the pulper and/or to the slurry passing into the flotation cell. Furnishes that may be deinked with the compounds of the instant invention include waste paper with laser print, printed waste paper for a newsprint mill, ink fixed on pulp fiber of the printed waste paper product such as newspaper and magazines, and flexo news/magazine/newsprint, and the like. The apparatus and processes for deinking operations in well-known to those of skill in the art. Typical apparatus and processes are disclosed in U.S. Patent Nos.
  • the amount of the compound of structural formula (1) is about 0.01 wt. % to about 2.0 wt. % , preferably about 0.03 wt. % to about 1.0 wt. % , and most preferably about 0.05 wt. % to about 0.5 wt. % of the dry fiber.
  • ethylene oxide/propylene oxide nonionic for example, alcohol or fatty acid alkylphenol derivatives
  • surfactant for frothing and foam control
  • sodium silicate sodium hydroxide
  • hydrogen peroxide or sodium hypochlorite and an EDTA or DTPA chelant
  • cationic deinking agents can be combined with fatty acids, alkylene oxide adducts, and other solvents. Deinking is usually conducted on fiber slurries of 1 % consistency at 40-50°C.
  • EXAMPLES 27 TO 31 ss These examples illustrate formulations of compounds according to structural formula (1) for use in personal care formulations, for example, for hair conditioners and skin conditioners.
  • Example 29 is a microemulsion example comparable to Example 14.
  • the component includes all similar compounds, that is, compounds where the ions are substituted by any other ion which is not significantly deleterious to the desired chemical or physical properties of the overall compound in its intended use. It is therefore understood that such ion substitution is well- known in the art and all such possibilities and equivalents are intended to be embraced within the appended claims. As noted above, the examples provided are intended to further describe the aspects of the present invention.

Abstract

L'invention concerne une composition renfermant a) un composé de formule développée (1), dans laquelle chaque R* et R** représente indépendamment un groupe alkylène linéaire, ramifié ou cyclique contenant entre 2 et 12 atomes de carbone où il n'existe pas deux atomes d'azote séparés par moins de 2 atomes de carbone; chaque A?1, A2, A3, A4 et A5¿ représente indépendamment un alkylène linéaire ou ramifié contenant entre 2 et 4 atomes de carbone; chaque R?1, R2, R3, R4 et R5¿ représente indépendamment H ou RA C(O) où RA représente un alkyle ou alcényle linéaire ou ramifié contenant entre 7 et 21 atomes de carbone et entre 0 et 4 doubles liaisons carbone-carbone; à condition qu'au moins un R?1, R2, R3, R4 ou R5¿ représente RAC(O); chaque Q?1, Q2 et Q3¿ représente indépendamment, CH¿3?, C2H5, C3H7, C4H5, benzyle, CH2COOH ou H2COOA?-¿; ou si R* représente un groupe H¿2?CH2-, Q?1 et Q3¿ pris ensemble ou Q1 et Q2 pris ensemble peuvent représenter un groupe H¿2?CH2- pour former un noyau de pipérazine à six chaînons; ou si R** représente un groupe H2CH2-, Q?3 et Q3¿ pris ensemble peuvent représenter un groupe H¿2?CH2- pour former un cycle de pipérazine à six chaînons; m représente une valeur comprise entre 0 et 4; r représente une valeur comprise entre 0 et 2, chaque v, w, x, y et z représente indépendamment une valeur comprise entre 1 et 8; i représente une valeur comprise entre 0 et 1, j une valeur comprise entre 0 et 1 et chaque k une valeur comprise entre 0 et 1. La somme entre (i+j+k) est égale à une valeur comprise entre 0 et 4. Chaque A?-¿ représente indépendamment un anion tel que défini ci-dessus et n représente le nombre de moles de A- nécessaire pour donner au composé de formule développée (1) une charge nette nulle. La composition renferme encore de l'eau et ne contient pas une quantité notable de composés ou silicones de traitement de résines textiles.
PCT/US1998/021683 1998-10-13 1998-10-13 Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation WO2000021918A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP98949809A EP1121341A1 (fr) 1998-10-13 1998-10-13 Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation
CA002347036A CA2347036A1 (fr) 1998-10-13 1998-10-13 Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation
PCT/US1998/021683 WO2000021918A1 (fr) 1998-10-13 1998-10-13 Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation
KR1020017004698A KR20010106516A (ko) 1998-10-13 1998-10-13 폴리에스테르 폴리쿼터너리 화합물, 이들을 함유한 조성물및 이들의 용도
AU96047/98A AU9604798A (en) 1998-10-13 1998-10-13 Polyester polyquaternary compounds, compositions containing them, and uses thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211140B1 (en) 1999-07-26 2001-04-03 The Procter & Gamble Company Cationic charge boosting systems
US6540822B2 (en) 2001-03-20 2003-04-01 Akzo Nobel N.V. Polybetaines as asphalt emulsifiers
US6752905B2 (en) 2002-10-08 2004-06-22 Kimberly-Clark Worldwide, Inc. Tissue products having reduced slough
US6808600B2 (en) 2002-11-08 2004-10-26 Kimberly-Clark Worldwide, Inc. Method for enhancing the softness of paper-based products
WO2013041986A2 (fr) 2011-09-21 2013-03-28 Kimberly-Clark Worldwide, Inc. Produit de papier d'essuyage comportant du bambou
WO2016134256A1 (fr) 2015-02-20 2016-08-25 Kimberly-Clark Worldwide, Inc. Papier ouaté comportant des résineux du sud des états-unis
US9868856B2 (en) 2014-12-05 2018-01-16 Akzo Nobel Chemicals International B.V. Polymer stabilizers for bituminous emulsions
CN111484835A (zh) * 2020-04-23 2020-08-04 新疆塔里木油田建设工程有限责任公司 一种水溶性油基钻井液润滑剂及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170938A (en) * 1957-05-31 1965-02-23 Wyandotte Chemicals Corp Surface active agents
DE3135014A1 (de) * 1981-09-04 1983-03-24 Hoechst Ag, 6000 Frankfurt Waescheweichspuelmittel
EP0242925A2 (fr) * 1986-04-21 1987-10-28 The Nisshin Oil Mills, Ltd. Huiles pour le laminage à froid pour tôles d'acier
US4743304A (en) * 1983-12-14 1988-05-10 Morton Thiokol, Inc. Asphalt antistripping agents containing organic amines and Portland cement
EP0360181A2 (fr) * 1988-09-22 1990-03-28 Hoechst Aktiengesellschaft Sels d'acides herbicides avec des bases azotées à longue chaîne
EP0461419A1 (fr) * 1990-06-12 1991-12-18 REWO Chemische Werke GmbH Esters de poly(oxyalkylène)aminoalkanols, leurs sels d'ammonium, procédés pour leur préparation et leur utilisation comme lessives, agents de nettoyage, désinfectants et conservateurs
JPH0718571A (ja) * 1993-06-29 1995-01-20 Lion Corp 柔軟剤組成物
EP0643038A2 (fr) * 1993-07-15 1995-03-15 Aranor, S.A. Agents de surface polyfonctionels cationiques, compositions les contenant, procédé de préparation et usages
WO1996003970A1 (fr) * 1994-08-05 1996-02-15 Witco Corporation Compositions traitantes quaternaires biodegradables pour les cheveux et la peau
EP0803498A1 (fr) * 1996-04-26 1997-10-29 Witco Corporation Composés de polyesters polyquaternaires, compositions les contenant et leur utilisation comme agents adoucissants

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170938A (en) * 1957-05-31 1965-02-23 Wyandotte Chemicals Corp Surface active agents
DE3135014A1 (de) * 1981-09-04 1983-03-24 Hoechst Ag, 6000 Frankfurt Waescheweichspuelmittel
US4743304A (en) * 1983-12-14 1988-05-10 Morton Thiokol, Inc. Asphalt antistripping agents containing organic amines and Portland cement
EP0242925A2 (fr) * 1986-04-21 1987-10-28 The Nisshin Oil Mills, Ltd. Huiles pour le laminage à froid pour tôles d'acier
EP0360181A2 (fr) * 1988-09-22 1990-03-28 Hoechst Aktiengesellschaft Sels d'acides herbicides avec des bases azotées à longue chaîne
EP0461419A1 (fr) * 1990-06-12 1991-12-18 REWO Chemische Werke GmbH Esters de poly(oxyalkylène)aminoalkanols, leurs sels d'ammonium, procédés pour leur préparation et leur utilisation comme lessives, agents de nettoyage, désinfectants et conservateurs
JPH0718571A (ja) * 1993-06-29 1995-01-20 Lion Corp 柔軟剤組成物
EP0643038A2 (fr) * 1993-07-15 1995-03-15 Aranor, S.A. Agents de surface polyfonctionels cationiques, compositions les contenant, procédé de préparation et usages
WO1996003970A1 (fr) * 1994-08-05 1996-02-15 Witco Corporation Compositions traitantes quaternaires biodegradables pour les cheveux et la peau
EP0803498A1 (fr) * 1996-04-26 1997-10-29 Witco Corporation Composés de polyesters polyquaternaires, compositions les contenant et leur utilisation comme agents adoucissants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 70, no. 24, 16 June 1969, Columbus, Ohio, US; abstract no. 107468f, BLACK W ET AL: "TEXTILE TREATMENT WITH CATIONIC AGENTS AND ELECTROLYTES" page 56; XP002036143 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6211140B1 (en) 1999-07-26 2001-04-03 The Procter & Gamble Company Cationic charge boosting systems
US6540822B2 (en) 2001-03-20 2003-04-01 Akzo Nobel N.V. Polybetaines as asphalt emulsifiers
US6752905B2 (en) 2002-10-08 2004-06-22 Kimberly-Clark Worldwide, Inc. Tissue products having reduced slough
US6808600B2 (en) 2002-11-08 2004-10-26 Kimberly-Clark Worldwide, Inc. Method for enhancing the softness of paper-based products
WO2013041986A2 (fr) 2011-09-21 2013-03-28 Kimberly-Clark Worldwide, Inc. Produit de papier d'essuyage comportant du bambou
US9868856B2 (en) 2014-12-05 2018-01-16 Akzo Nobel Chemicals International B.V. Polymer stabilizers for bituminous emulsions
WO2016134256A1 (fr) 2015-02-20 2016-08-25 Kimberly-Clark Worldwide, Inc. Papier ouaté comportant des résineux du sud des états-unis
CN111484835A (zh) * 2020-04-23 2020-08-04 新疆塔里木油田建设工程有限责任公司 一种水溶性油基钻井液润滑剂及其制备方法

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EP1121341A1 (fr) 2001-08-08
KR20010106516A (ko) 2001-11-29
CA2347036A1 (fr) 2000-04-20

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