Classifications

• • 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
  • C11D1/38—Cationic compounds
  • C11D1/60—Sulfonium or phosphonium 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
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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
  • C11D1/66—Non-ionic compounds
  • C11D1/835—Mixtures of non-ionic with cationic compounds

Definitions

• This invention relates to laundry detergent compositions containing no or low levels of phosphate materials, which exhibit highly improved particulate soil removal capabilities. These detergent compositions provide surprisingly effective clay soil removal performance even in the absence of detergency builders.
• Nonionic surfactants are generally used in laundry detergent compositions for their ability to remove greasy and oily soils. Cationic surfactant have also been used in detergent compositions, to provide adjunct fabric care benefits, and not for the purpose of cleaning. Certain cationic surfactants have been included in detergent compositions for the purpose . of yielding a germicidal or sanitization benefit to washed surfaces; see, for example, U.S. Patent 2,742,434, Kopp, issued April 17, 1956; U.S. Patent 3,539,520, Cantor et al, issued November 10, 1970; and U.S. Patent 3,965,026, Lancz, issued June 22, 1976.
• cationic surfactants such as ditallowalkyldimethylammonium chloride
• detergent compositions for the purpose of yielding a fabric- softening benefit, as disclosed in U.S. Patent 3,607,763, Salmen et al, issued September 21, 1971; and U.S. Patent 3,644,203, Lamberti et al, issued February 22, 1972.
• Such components are also used to control static, as well as soften laundered fabrics as, for example, in U.S. Patent 3,951,879, Wixon, issued April 20, 1976; and U.S. Patent-3,959,157, Inamorato, issued May 25, 1976. All of the above patents being incorporated herein by reference.
• compositions of the present invention have outstanding cleaning capabilities. In laundry tests, these compositions, not containing any builder components, have been shown to remove clay soils at least as well, and in some cases dramatically better, than fully-built conventional laundry detergent compositions.
• the compositions inhibit the transfer of dyes, soften and control static through the washing and drying operations-Further, by selecting the preferred cationic components defined in this application, the compositions additionally provide biodegradability and excellent removal of greasy and oily soils, while also providing, in a single detergent product, particulate soil removal, fabric softening, static control and dye transfer inhibition benefits to the laundered fabrics.
• the cleaning performance which is superior to that previously demonstrated, is the result of a heretofore unrecognized cleaning potential of certain selected cationic surfactants when used in the presence of certain selected nonionic surfactants under the conditions specified herein.
• the present invention relates to laundry detergent compositions, containing from 0 to about 20% phosphate materials, which are especially beneficial for the removal of particulate soils from fabrics, having a pH of at least about 6.5 in the aqueous laundry solution, and which are substantially free of fatty acid polyglycol ether diester compounds, oily hydrocarbon materials and cationic materials containing 13 or more ethylene oxide groups, comprising from about 5 to about 100%, by weight, of a surfactant mixture consisting essentially of
• compositions of the present invention are formulated so as to have a pH of at least about 6.5 in the laundry solution at conventional usage concentrations in order to optimize overall cleaning performance; preferably, they are alkaline in nature (pH greater than about 7) when placed in the laundry solution, and preferred compositions have a pH of at least about 7.5.
• Some of the cationic/ nonionic systems of the present invention will attain optimum removal of greasy/oily soils at higher pHs, while attaining optimum clay removal at relatively lower pHs. In these systems, overall performance may be enhanced by varying the pH of the wash solution during the laundering process.
• Particularly preferred compositions have a pH of at least about 8 in the laundry solution, in order to improve the removal of bodv soil. In addition to the alkaline laundry solution pH.
• these preferred compositions should also have the ability to maintain a pH in the laundry solution of from about 8 to 11 throuahout the washing operation (reserve alkalinitv).
• a reserve alkalinity may be obtained bv incorooratina comoounds which buffer at pHs of from about 8 to 11. such as monoethanolamine diethanolamine or triethanolamine.
• compositions are free of oily hydrocarbon materials, such as dry cleaning solvents mineral oil, paraffin oil and kerosene, because these materials (which are themselves oily in nature) load the washing liquor with excessive oily material, thereby diminishing the cleaning effectiveness of the compositions of the present invention.
• oily hydrocarbon materials such as dry cleaning solvents mineral oil, paraffin oil and kerosene
• the cationic component is free of hydrazinium groups due to their relatively high toxicity level which makes them unsuitable for use in the compositions of this invention.
• compositions of the present invention are substantially free of fatty acid polyglycol ether diester compounds, such as polyethylene glycol-600-dioleate or polyethylene glycol-800-distearate.
• fatty acid polyglycol ether diester compounds such as polyethylene glycol-600-dioleate or polyethylene glycol-800-distearate.
• compositions contain nonionic surfactant to cationic surfactant ratios of from 5:1 to about 5:3, especially from about 10:3 to 10:5, and particularly about 10:4.
• Compositions may also contain mixed nonionic systems. These mixed nonionic systems may contain nonionic surfactants contain nonionic surfactants which fall outside of the definition of the nonionic surfactant given above (such as alcohol polyethoxylates having an average of greater than 12 ethylene oxide groups molecule) as long.as at least one of the nonionic surfactants in the mixture falls within the required definition and the ratio of that nonionic surfactant to the cationic surfactant falls within the required nonionic:cationic surfactant ratio.
• compositions may also contain fatty amide surfactants, in addition to the cationic and nonionic components. These amide-containing compositions yield excellent particulate soil removal, as well as a particulate soil anti-redeposition benefit. Processes for laundering fabrics with the compositions of the present invention are also taught herein.
• compositions of the present invention comprise, by weight, from about 5 to about 100 %, particularly from about 10 to about 95%, and most preferably from about 20 to about 90 %, of a mixture of the particularly defined nonionic and cationic surfactants in the ratios stated. It is preferred that the detergent compositions contain at least 1 % of the cationic component; otherwise, sufficient cationic surfactant may not be present in the wash solution to provide the desired cleaning results. Compositions containing 10 %-or more of the cationic component are not encompassed within the present invention. Such large amounts of cationic surfactant are impractical due to commercial availability and cost considerations.
• the nonionic surfactants used in the compositions of the present invention are biodegradable and have the formula wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to 18, carbon atoms and n is an average of from about 2 to about 12, preferably from about 2 to about 9, most preferably from about 2 to about 7, and especially from about 4 to about 7.
• the nonionic surfactants included within the present invention include branched alcohol ethoxylates.
• the nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 14. Especially useful particulate soil removal can be obtained with nonionic surfactants having HLBs of from about 10 to about 13.5.
• nonionic surfactants are preferably combined with less soluble cationic materials (such as those having 2 or 3 long alkyl chains). Where more soluble cationic materials are used, nonionic surfactants of lower HLB may be equally as beneficial. HLB is defined in detail in Nonionic Surfactants, by M.J. Schick, Marcel Dekker, Inc., 1966, pp. 607-613, incorporated herein by reference.
• Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C 10 alcohol with 3 moles of ethylene oxide, the condensation product of coconut alcohol with 5 moles of ethylene oxide, the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C 12-13 alcohol with 3 moles of ethylene oxide, and the same product which is stripped so as to remove the lower ethoxylate and nonethoxylated fractions, the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide, the condensation product of C 12 alcohol with 5 moles of ethylene oxide, the condensation product of C 12-13 alcohol with 9 moles of ethylene oxide, the condensation product of C14-15 alcohol with 3 moles of ethylene oxide,.
• a preferred class of such surfactants are made from substantially linear alcohols, such as those which utilize oxoalcohols containing about 20% 2-methyl branched isomers, commercially available under the tradename Neodol, from Shell Chemical Company.
• compositions of the present invention may also contain mixtures of nonionic surfactants falling within the above nonionic surfactant definition, or mixtures of nonionic surfactants, some of which do not fall within the above nonionic surfactant definition, as long as at least one of the nonionic surfactants contained in the mixture falls within the above definition of the nonionic surfactants, and the ratio of that nonionic surfactant to the cationic surfactant falls within the required nonionic/cationic ratio.
• the ratio of the surfactant (or surfactants) within the above definition to that which docs not fall within the definition is preferably within the range of from about 1:1 to about 5:1.
• surfactant mixtures include a mixture of the condensation product of C 14-15 alcohol with 3 moles of ethylene oxide (Neodol 45-3) and the condensation product of C 14-15 alcohol with 14 moles of ethylene oxide (Neodol 45- 14 ), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; a mixture of the condensation product of C 10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C 15 alcohol with 9 moles of ethylene oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 4:1; and a mixture of Neodol 45-3 and Tergitol 15-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1.
• Preferred nonionic surfactant mixtures contain alkyl glyceryl ether compounds in addition to the required nonionic surfactant.
• biodegradable nonionic surfactants well known in the detergency arts may be used, in combination with one or more of the nonionic surfactants falling within the definition of nonionic surfactants required in the present invention, to form useful nonionic surfactant mixtures.
• examples of such surfactants are listed in U.S. Patent 3,717,630, Booth, issued February 20, 1973, and U.S. Patent 3,332,880, Kessler et al, issued July 25, 1967, each of which is incorporated herein by reference.
• suitable nonionic surfactants which may be used in conjunction with the required nonionic surfactants include the condensation products of aliphatic alcohols with from about 13 to about 25 moles of ethylene oxide.
• the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
• ethoxylated alcohols include the condensation product.of myristyl alcohol condensed with about 13 moles of ethylene oxide per mole of alcohol; and the condensation product of about 14 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
• each R 1 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with' up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the following group: and mixtures thereof, and which contains from about 8 to 22 carbon atoms.
• the R 1 groups may additionally contain up to 12 ethoxy groups.
• m is a number from 1 to 3. No more than one R 1 group in a molecule can have 16 or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3.
• Each R 2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 2 in a molecule being benzyl, and x is a number from 0 to 11, preferably from 0 to 6 The remainder of any carbon atom positions on the Y group are filled by hydrogens.
• Y is selected from the group consisting of: wherein p is from 1 to 12, wherein each p is from 1 to 12, and (9) mixtures thereof;
• these cationic components When used in combination with nonionic surfactants, within the specific ratios and the preferred reduced cationic monomer concentrations, defined hereinafter, these cationic components provide excellent soil removal characteristics, confer static control and fabric softening benefits to the laundered fabrics, and inhibit the transfer of certain dyes among the laundered fabrics in the wash solution.
• Preferred cationic surfactants are those which have critical micelle concentrations less than about 500 ppm.
• L is equal to 1 and Y is or mixtures thereof.
• L may be 2 and, in that case, the cationic component contains 2 cationic charge centers.
• of the present invention include phosphonium and.sulfonium materials.
• compositions of this mono-long chain type include those in which R 1 is a C 10 to C 18 alkyl group.
• Particularly preferred compositions of this class include C 12 alkyl trimethylammonium halide, C 14 alkyl trimethylammonium halide, coconutalkyl trimethylammonium halide, tallowalkyl trimethylammonium halide, and C 16 alkyl trimethylammonium halide.
• the cationic surfactant In order to be sufficiently water-soluble or water-dispersible, the cationic surfactant must satisfy the following chain-length criteria. Where m is equal to 2, only one of the R 1 chains can be longer than 16 carbon atoms. Thus, ditallowdimethylammonium chloride and di- stearyldimethylammonium chloride, which are used conventionally as fabric softeners and static control agents in detergent compositions, are not included within the definition of the cationic components used in the present invention.
• Preferred di-long chain cationics of this type include those in which x is equal to 2 and R 2 is a methyl group. In this instance it is also preferred that R 1 is a C 10 to C 14 alkyl group. Particularly preferred cationic materials of this class include di-C 10 alkyldimethylammonium halide, di-C 12 alkyldimethylammonium halide materials, and dicoconutalkyl dimethylammonium halide.
• R 1 is a C 8 to C 12 alkyl group.
• Particularly preferred tri-long chain cationics include trioctylalkylmethylammonium halide, and tridecylalkyl- methylammonium halide.
• compositions of the present invention arc the alkoxylated alkyl quaternaries.
• alkoxylated alkyl quaternaries examples of ethoxylated compounds are given below: wherein each p is from 1 to 12, preferably from 1 to 10, most preferably from 1 to 7, with the total ethylene oxide groups in a molecule not exceeding about 12.
• Each R is a C 10 to C 20 alkyl group.
• compositions of the present invention are formulated so as to be substantially free of ethoxylated cationic surfactants which contain an average of about 13 or more, and especially more than-about 10, moles of ethylene oxide per mole of surfactant. These compounds tend to be relatively nonbiodegradable, do not enhance the cleaning or fabric conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them.
• a particularly preferred type of cationic component has the formula wherein R 1 is C 1 to C 4 alkyl or hydroxyalkyl; R 2 is C 5 to C 30 straight or branched chain alkyl or alkenyl, alkyl phenyl, or wherein s is from 0 to 5; R 3 is C 1 to C 20 alkylene or alkenylene; a is 0 or l, n is C or 1, and n is 1 when a is 1; m is from 1 to 5; Z 1 and Z 2 are each selected from the group consisting of and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, and nitrate, preferably chloride, bromide, iodide, sulfate, or methyl sulfate.
• this particular cationic component is environmentally desirable, since it is biodegradable, yielding environmentally acceptable compounds, both in terms of its long alkyl fragment and nitrogen-containing fragment.
• the detergent compositions have a pH of not greater than about 11, preferably less than about 10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.
• Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula: as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
• p may be from 0 to 20.
• the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternizcd with a methyl halide, forming the desired cationic material.
• the choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
• each R 1 is a C 1 to C 4 alkyl or hydroxy- alkyl group, preferably a methyl group.
• Each R 2 is either hydrogen or C 1 to C 3 alkyl, preferably hydrogen.
• R 3 is a C 4 to C 30 straight or branched chain alkyl, alkenyl, alkyl phenyl, or alkyl benzyl group, preferably a C 8 to C 18 alkyl group, most preferably a C 12 alkyl group.
• R is a C 1 to C 10 alkylene or alkenylene group.
• n is from 2 to 4, preferably 2; y is from 1 to 20, preferably from about 1 to 10, most preferably about 7; a may be 0 or 1, and t may be 0 or 1, but t must be 1 when a is 1; and m is from 1 to 5, preferably 2.
• Z 2 is selected from the group consisting of: Z 1 is selected from the group consisting of: and wherein at least one of said Z 1 and Z 2 groups is selected from the group consisting of ester, reverse ester, amide and reverse amide.
• X is an anion which will make the compound at least water-dispersible, and is selected from the group consisting of halides, methyl sulfate, and nitrate, particularly chloride, brimide, iodide, sulfate, sulfate. Mixtures of the above structures can also be used
• these surfactants when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal.
• the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of certain dyes in the washing solution.
• these novel cationic surfactants are environmentally desirable, since both their long chain alkyl fragments and their nitrogen fragments are biodegradable, in that they degrade to yield environmentally acceptable compounds.
• the detergent compositions have a. pH-of not greater than about 11, preferably less than about 10, in the laundry solution, in order to minimize hydrolysis of the cationic surfactant.
• Preferred embodiments of this type of cationic component are the esters in which R 1 is a methyl group and Z 2 is an ester or reverse ester group, particular formulas of which are given below, in wchich t is 0 or 1 and y is from 1 to 20.
• the preferred derivatives, described above, may be prepared by the reaction of a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride.
• the acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound.
• Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst.
• the reaction product formed is then quaternized with methylhalide or used to quaternize trimethylamine to form the desired choline ester compound.
• the reduced cationic monomer concentration may be used.
• the nonionic and cationic components defined above, may be combined into a surfactant mixture which has a ratio corresponding to a reduced cationic monomer concentration (C R ) of from about 0.005 to about 0.2, preferably from about 0.008 to about 0.15, particularly from about 0.01 to about 0.1.
• C R reduced cationic monomer concentration
• a C R value within this range will yield a composition which exhibits optimum particulate soil removal performance.
• the nonionic and cationic components used are pure, the more narrow C R ranges are preferred. In a preferred method of .
• the nonionic and cationic surfactants are intimately and completely mixed together prior to the addition of anv additional components to the mixture. This intimate premixing of the nonionic and cationic components enhances performance of the compositions.
• C R critical micelle concentration
• x was found by inserting the values known from the test (i.e., c * 1 , c * 2 , ⁇ , C and ⁇ ) into equation (1) and solving iteratively for x, such that the error in x is less than 0.001. This procedure was repeated for a large number of such tests, over varying usage conditions. The x values obtained were then used to solve for the cationic monomer concentrations using the following equation: The C value was then calculated using equation (3).
• the C R values obtained cover a large number of combinations and ratios of various nonionic and cationic surfactants, at various concentrations and temperatures, which have been evaluated for their ability to clean greasy/oily soils.
• the examination of the resulting data revealed that for a given system the optimum cleaning of greasy/oily soils was found at a C R value of from about 0.002 to about 0.2.
• This range of C R (i.e., 0.002 to 0.2) can then be used to determine the range of optimum nonionic/cationic vrios for any given combination of nonionic surfactant and cationic surfactant, for the desired wash concentration within the overall wash concentration range of from 100 parts per million (ppm) to 10,000 ppm of surfactant.
• This calculation is carried out in the following manner, where ⁇ , C R , c* 1 , c* 2 , M 1 and M 2 are known for a given nonionic/ cationic surfactant pair:
• steps (b) and (c) may be combined . into a single equation which may be solved directly for the NCR.
• C R is essentially independent of concentration.
• the CR of most commercial cationic/ nonionic surfactant mixtures will be independent of the actual usage concentration, so that using a concentration of about 1,000 ppm in the above calculation will be a satisfactory approximation for the entire range.
• the 1,000 ppm C R is meant.
• the nonionic/cationic surfactant mixture may also satisfy the specific cloud point requirements, given below.
• these preferred compositions will be optimized for the removal of greasy/oily soils.
• the cloud point of the nonionic/cationic mixture falls between about 0 and about 95°C, preferably between about 10 and about 70°C, more preferably between about 20 and about 70 °C, especially between about 30 and about 50°C.
• the surfactant mixture should have a cloud point between about 0 and about 25°C.
• compositions have a cloud point within these temperature ranges assures that the composition can be utilized under laundry temperature conditions to achieve outstanding removal of greasy/oily soils. If a composition does not have a cloud point within the temperature range specified, it will not yield outstanding greasy/oily soil cleaning within that temperature range.
• the compositions will exhibit their best grease/oil removal-performance when'the temperature of the wash solution in which they are .used falls within about 20°C, preferably within about 15°C, and most preferably.within about 10°C, of the cloud point of the nonionic/cationic surfactant mixture.
• the laundry solution temperature range in which the preferred compositions deliver optimum grease/oil removal lies between the cloud point-temperature of the system in the absence of .the cationic component, and about 30°C, preferably about 25°C, most preferably about 20°C, above that cloud point temperature.
• cloud point means the temperature at which a graph which plots the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions:
• the light scattering intensity is'measured using a Model VM-12397 Photogoniodiffusometer, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (SOFICA).
• SOFICA sample cell and its lid are washed with hot acetone and allowed to dry.
• the surfactant mixture is made and put into solution with distilled water at a concentration of 1000 ppm. Approximately a 15 ml. smaple of the solution is placed into the sample cell, using a syringe with a 0.2 ⁇ nucleopore filter. The syringe needle passes through the sample cell lid, so that the cell interior is not exposed to atomospheric dust.
• the sample is kept in a variable temperature bath, and both the bath and the sample are subject to constant stirring.
• the bath temperature is heated using the SOFICA's heater and cooled by the addition of ice (heating rate 1°C/minute); the temperature of the sample is determined by the temperature of the bath.
• the light scattering intensity of the sample is then determined at various temperatures, using a green filter and no polarizer in the SOFICA.
• the nonionic surfactant/cationic surfactant mixture additionally contains from about 2 to about 25%, preferably from about.2 to about 16%, and most preferably from about 3 to about 10%, of a fatty amide surfactant.
• the ratio of the total cationic and nonionic components to the amide component in the composition is in the range of from 5:1 to about 50:1, preferably from about 8:1 to 25:1. when these compositions are formulated in accordance with the ratio and the preferred reduced cationic monomer concentration limits given herein, they result in excellent particulate soil removal performance, as well as improved soil anti-redeposition characteristics.
• Amides useful in these preferred compositions include, but are not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides.
• Preferred amides include those having the formulae: . wherein R 1 is a C 8 -C 20 alkyl, alkenyl, alkyl phenyl or alkyl group, preferably C 10- C 1 8 alkyl, and most preferably C 11 alkyl; and each R 2 is hydrogen, or C 1 - C 8 alkyl or hydroxyalkyl,preferably hydrogen.
• compositions of the present invention may contain additive materials conventionally used in detergent compositions, the amount of anion-producing materials, and hence. anions, which will make the particular cationic surfactant used in the compositions non-water dispersible should be minimized. Whether a particular anion constitutes-an "interfering anion" depends upon the physical and chemical properties (such as structure and dissociation constant) of the particular anions and cationic surfactants used in a given composition.
• anionic materials be contained in amounts sufficiently small such that not more than about 10 molar percent, preferably not more than about 5 molar percent, of the cationic surfactant contained in the laundry solution, is complexed by the anionic material Such a complexing of the anionic material with-the cationic surfactant decreases the overall cleaning and fabric conditioning performance of the composition.
• Suitable anionic materials may be selected based on their strength of complexation with the cationic material included in the composition (as indicated by their dissociation constant).
• an anionic material has a dissociation constant of at least about 1x10 -3 (such as sodium toluene sulfonate)
• it may be contained in an amount up to about 40%, by weight, of the cationic surfactant
• the anionic material has a dissociation constant of at -5 -3 least about 1x10 -5 , but less than about 1x10 -3 , it may be contained in an amount up to about 15%, by weight, of the cationic surfactant
• the anionic material has a dissociation constant of less than about 1x10 -3 , (such as sodium C 11-8 linear alkylbenzene sulfonate)
• it should be contained only in amounts up to about 10%, by weight, of the cationic surfactant.
• compositions of the present invention be substantially free of phosphate, polyphosphate, silicate, and polycarboxylate builder anions, carboxymethyl cellulose, and anionic surfactants; particularly preferred are those which are substantially free of phosphate, polyphosphate, and carboxymethyl cellulose materials.
• the compositions of the present invention contain from 0 to about 20% of phosphate materials; and, even though they contain no or low levels of phosphate materials, exhibit an outstanding level of particulate soil removal. It is preferred that the compositions be substantially free of phosphate materials both for performance and environmental reasons.
• compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, consistent with the restrictions on interfering anions, stated above, at their conventional art-established levels.
• Very low levels i.e., from about 1 to about 15%
• electrolytes such as perborates, phosphates, polyphosphonates, carbonates or sulfates, may.have a beneficial effect on cleaning performance.
• compositions of the present invention may contain up to about 15%, preferably up to about 5%, and most preferably from about .1 to 2%, of a suds suppressor component.
• Typical suds suppressors include long chain fatty acids, such as those described in U.S. Patent 2,954,347, issued September 27, 1960, St. John, and combinations of certain nonionics therewith, as disclosed in U.S. Patent 2,954,346,. issued September 2.7, 1960, .Schwoeppe, both disclosures being' incorporated herein by reference.
• Other suds suppressor components useful in the compositions of the present invention include, but are not limited to, those described below.
• the silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
• the silicone material can be described as a siloxane having the formula: wherein x is from about 20 to about 2,000, and R and .
• R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
• the polydimethylsiloxanes (R and R' are methyl) having a molecular weighl within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents.
• Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exchibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-ethyl-, phenylmethyl-polysiloxanes and the like.
• Additonal useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
• a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanted) silica having a particle size in the range from about 10.millimicrons to 20 millimicrons and a specific surface are above about 50 m 2 /gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2.
• the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
• Particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, such as DB-544, commercially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
• Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, such waxes are described in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incorporated herein by reference.
• the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic sufactants.
• Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the range from.400-1,000; and a penetration value of at least 6, measured at 77°F by ASTM-D1321.
• Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized . Fisher-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
• Alkyl phosphate esters represent an additional pref- erred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di-and trioleyl phosphates.
• alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g., monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate
• adjunct components which may be included in the compositions of the present invention, . in their conventional art-established levels of use, include bleaching agents, bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents,enzymes, enzyme stabilizing agents, perfumes, fabric softening components, static control agents, and the like.
• bleaching agents bleach activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents,enzymes, enzyme stabilizing agents, perfumes, fabric softening components, static control agents, and the like.
• many components such as static control agents, fabric softening agents and germicides, will not usually be necessary.
• compositions of the present invention may be manufactured and used in a variety of physical forms, such as solid, powder, granular, paste, or liquid.
• the compositions are particularly well-suited for incorporation into substrate articles for use in the home laundering process. These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about 3 to 120 grams, particularly from about 20 to 80 grams, of the detergent compositions of the present invention.
• a particularly preferred substrate article incorporates a bleaching component and a bleach activator on the substrate, together with the nonionic/cationic surfactant mixture.
• the specifically defined nonionic and cationic surfactants are intimately and completely mixed at a temperature of from about 25°C to about 95°C, preferably from about 40°C to about 90°C, prior to the addition of any additional components.
• the components are taken from their original liquid or powder form and are made into a thick paste, which is ideally suited for use in the substrate articles, described above.
• the components are present in nonionic:cationic ratios.of from 5:1 to about 1:1, preferably from 5:1 to about 5:3, and more preferably from about 10:3 to about 10:5, and are formed into mixtures which satisfy the reduced cationic monomer concentration requirements, herein.
• the components are intimately mixed together at a temperature of about 25°C.
• the anion contained in the cationic surfactant be bromide.
• the components are intimately mixed together at a temperature of at least about 65°C.
• the anion contained in the cationic surfactant be chloride.
• stearoyl choline chloride a powder, is intimately mixed at a temperature of about 80°C with the condensation product of C 12 alcohol with 5 moles of ethylene oxide, a liquid, at a nonionic:cationic ratio of about 10:4, a thick paste product is formed. If the same components are mixed together at about 25°C the mixture remains a liquid, which is much lass desirable for use in making substrate articles. Substantially similar results are obtained when the nonionic surfactant is the condensation product of coconut alcohol with 5 moles of ethylene oxide.
• compositions of the present invention are used in the laundering process by forming an aqueous solution (preferably one having a temperature of from about 10 to about 50°C). containing from about 0.01 (100 parts per million) to 0.3% (3,000 ppm), preferably from about 0.02 to 0. 2 %, and most preferably from about 0.03 to about 0.15%, of the nonionic/cationic detergent mixture, and agitating the soiled fabrics in that solution.
• the fabrics are then rinsed and dried.
• the compositions of the present invention yield exceptionally good particulate soil removal performance.
• the compositions also provide fabric softening, static control, and dye transfer inhibition benefits to the fabrics laundered therewith.
• the clay removal mechanism is as follows. At the optimum nonionic:cationic ratio, as defined by the reduced cationic monomer concentration, the cationic surfactant adsorbs onto the clay soil (negatively-charged) in a mono-layer, neutralizing the charge. This neutralized charge results in a hydrophobic surface which increases the adsorption of the nonionic surfactant onto the clay surface. The clay soil is then easily removed by the agitation.
• a threshhold concentration of at least about 50, preferably about 100, most preferably about 150, parts per million on the cationic component must be present in the laundry solution in order to give the particulate soil removal benefit.
• nonionic surfactant to cationic surfactant ratios of from 5:1 to about 1:1 are necessary in order to provide this threshhold concentration in the laundry solution.
• a detergent composition of the present invention has the following formulation:
• This detergent composition having a nonionic: cationic ratio of about 10:4, was used in the aqueous laundering solution at a concentration of about 500 ppm, and had a pH in the laundry solution of about 6.5.
• the composition had outstanding clay soil removal performance.
• a laundry detergent composition of the present invention has the following formulation:
• the detergent composition of the present inven- t ion had a ratio of nonionic surfactant to cationic surfactant of about 10:4 and was used in the aqueous laundering solution at a concentration of about 500 ppm, having a pH in the laundry solution of about 6.5.
• the detergent composition of the present invention yields excellent particulate soil removal performar.ce,,good grease and oil removal, and gives fabric softening, static control and dye transfer inhibition benefits to fabrics laundered therewith.
• This detergent composition had a pII in the wash'solution of about 8.5, and was used in the washing solution at a concentration of about 500 ppm.
• a second detergent composition of the present invention was formulated by combining the same nonionic and cationic surfactants in the same ratio as above.
• the composition also contained monoethanolamine as an alkalinity source, in an amount such that the monoethanolamine was present at about 30 ppm in the washing solution when the entire composition was used at a concentration of about 530 ppm.
• the pH of the second detergent composition in the laundry solution was about 9.3.
• Identical polyester/cotton blend swatches were stained with a mixture of soil collected from air conditioning filters and a mineral oil/olive oil/oleic acid blend. The stained swatches were then washed using each of the above two detergent compositions in a one gallon washing machine which simulates the action of a commercial washing machine. The washing operation was carried out for 10 minutes using water having a temperature of about 100°F (38°C) and containing 7 grains per gallon of mixed calcium and magnesium hardness.
• the soil removal performance was calculated by using the weight removal percentage, averaged across the three stained swatches washed in each composition. Both compositions gave excellent soil removal performance. However, the cationic/nonionic mixture containing monoethanolamine and having the higher. alkalinity had a soil removal of about 73%, while the lower pII cationic/nonionic mixture had a soil removal of about 50%. These data demonstrate that improved soil removal performance is obtained by the use of cationic/nonionic detergent compositions having a higher alkalinity such as that obtained by the inclusion of monoethanolamine.
• a detergent composition of the present invention was formulated by combining the condensation product of coconut alcohol with 5 moles of ethylene oxide together with the cationic surfactant having the formula: such that the ratio of nonionic surfactant to cationic surfactant was about 10:4.
• the detergent composition was used in the laundry solution at a concentration of about 500 ppm.
• a second.detergent composition of the present invention was formulated so as to contain the same nonionic and cationic components in the same ratio, but which additionally contained a C 12-16 alkyl fatty acid ammonia amide, present in an amount such that the amide component would be present in the washing solution at a concentration of 50 ppm when the composition was used at a concentration of 500 ppm. This composition had a pH in the laundry solution of about 8.4.
• the nonionic component is replaced by a mixture of the condensation product of C 10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C 15 .alcohol with 9 moles of ethylene oxide, in a ratio of lower ehoxylate nonionic to-higher ethoxylate nonionic of about 3:1; or the mixture of the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkyl glyceryl ether having the formula: wherein the ratio of nonionic surfactant to glyceryl
• a solid particulate detergent composition of the present invention having the formulation given below, is made by mixing together the following componements.

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• 1978
  • 1978-06-28 GB GB7925946A patent/GB2040985B/en not_active Expired
  • 1978-06-28 IT IT25097/78A patent/IT1097132B/it active
  • 1978-06-28 DE DE19782857164 patent/DE2857164A1/de not_active Withdrawn
  • 1978-06-28 EP EP78200064A patent/EP0000234A1/en not_active Withdrawn
  • 1978-06-29 BR BR787804160A patent/BR7804160A/pt unknown
  • 1978-06-29 AU AU37594/78A patent/AU525487B2/en not_active Expired
• 1979
  • 1979-05-25 FR FR7913433A patent/FR2428073A1/fr active Granted

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