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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
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  • 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
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  • 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
  • C11D1/645—Mixtures of compounds all of which are cationic
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  • 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
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  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2044—Dihydric alcohols linear
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  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2048—Dihydric alcohols branched
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  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2093—Esters; Carbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/34—Organic compounds containing sulfur
  • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
  • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
  • C22F1/18—High-melting or refractory metals or alloys based thereon
  • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
  • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• • 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
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
• • 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
  • C11D1/58—Heterocyclic 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
  • C11D1/74—Carboxylates or sulfonates esters 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
  • C11D1/75—Amino oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols

Definitions

• the present invention relates to specific clear or translucent fabric softener compositions.
• clear, or translucent liquid compositions are prepared with high electrolyte levels to provide a dilution viscosity benefit and/or to allow the use of less and/or additional principal solvents as described hereinafter.
• the compositions can also contain an optional phase stabilizer, e.g., nonionic, ethoxylated cationic, etc. surfactant to improve properties.
• the fabric softener actives in said patents are preferably biodegradable ester-linked materials, containing, long hydrophobic groups with unsaturated chains. Similar clear liquid fabric softening compositions are described in WO 97/03169, incorporated herein by reference, which describes the formulation of liquid fabric softening compositions using said specific principal solvents.
• the gelling and/or increased viscosity upon dilution is particularly unacceptable when it occurs between the dilution ratios of from about 1:1 to about 1 :5 (fabric softener composition to water) since many consumers practice the habit of pre-diluting fabric softener compositions to these ratios. This habit is typical and is recommended by many washing machine manufacturers for consumers using the automatic dispensing device supplied with their washing machine.
• Increased viscosity or gelling of the fabric softener upon dilution can adversely affect the dispersion of the fabric softener composition in the rinse, resulting in poor performance, including an increase in fabric staining incidents.
• the clear, or translucent liquid fabric softener compositions herein comprise: A. from about 2% to about 80%, preferably from about 13% to about 75%, more preferably from about 17% to about 70%, and even more preferably from about 19% to about 65%, by weight of the composition, of fabric softener active, more preferably biodegradable fabric softener actives as disclosed hereinafter.
• the phase transition temperature of the softener active or mixture of actives, containing less than 5% organic solvent or water, is preferably less than 50°C, more preferably less than about 35°C, even more preferably less than about 20°C, and yet even more preferably less than about 10°C, or is amorphous and has no significant endothermic phase transition in the region -50°C to 100°C, as measured by differential scanning calorimetry as disclosed hereinafter.
• B at least an effective level of principal solvent preferably having a ClogP of from about -2.0 to about 2.6 , more preferably from about -1.7 to about 1.6, and even more preferably from about -1.0 to about 1.0, as defined hereinafter, typically at a level that is less than about 40%, preferably from about 1% to about 25%, more preferably from about 3% to about 10% by weight of the composition;
• D optionally, but preferably, from 0% to about 15%, preferably from about 0.1% to about 7%, and more preferably from about 1% to about 6%, by weight of the composition of phase stabilizer, preferably surfactant containing alkoxylation, and also preferably having an HLB of from about 8 to about 20, more preferably from about 10 to about 18, and even more preferably from about 11 to about 15, and more preferably as described hereinafter; and
• the clear, or translucent liquid fabric softener compositions can optionally also contain: (a) optionally, but preferably, from 0% to about 15%, more preferably from about 0.1% to about 8%, and even more preferably from about 0.2% to about 5%, of perfume;
• compositions herein are aqueous, translucent or clear, preferably clear, compositions containing from about 10% to about 95%, preferably from about 20% to about 80%, more preferably from about 30% to about 70%, and even more preferably from about 40% to about 60%, water.
• These products (compositions) are usually not translucent or clear without principal solvent B.
• the principal solvent and/or electrolyte levels, as well as the identity of the principal solvent, are related to the level and identity of the softener.
• the electrolyte and phase stabilizer are typically used at the lowest level that will provide the desired result.
• the pH of the compositions should be from about 1 to about 5, preferably from about 2 to about 4, and more preferably from about 2.7 to about 3.5.
• Typical levels of incorporation of the softening compound (active) in the softening composition are of from 2% to 80% by weight, preferably from 5% to 75%, more preferably from 15% to 70%, and even more preferably from 19% to 65%, by weight of the composition, and preferably is biodegradable as disclosed hereinafter.
• the phase transition temperature of the softener active or mixture of actives, containing less than 5% organic solvent or water is less than 50°C, more preferably less than about 35°C, even more preferably less than about 20°C, and yet even more preferably less than about 10°C, or is amorphous and has no significant endothermic phase transition in the region -50°C to 100°C.
• the phase transition temperature can be measured with a Mettler TA 3000 differential scanning calorimeter with Mettler TC 10A Processor.
• the softening compound can be selected from cationic, nonionic, and/or amphoteric fabric softening compounds.
• Typical of the cationic softening compounds are the quaternary ammonium compounds or amine precursors thereof as defined hereinafter.
• the first type of DEQA preferably comprises, as the principal active, [DEQA (1)] compounds of the formula
• each R substituent is either hydrogen, a short chain Cj-Cg, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, poly (C2-.3 alkoxy), preferably polyethoxy, group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably 2; each Y is -O-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)-NR-; the sum of carbons in each R 1 , plus one when Y is -O-(O)C- or -NR-C(O) -, is C12-C22, preferably C14-C20, with each R 1 being a hydrocarbyl, or substituted hydrocarbyl group, and X" can be any softener-compatible anion,
• DEQA (2) A second type of DEQA active [DEQA (2)] has the general formula:
• each R is a methyl or ethyl group and preferably each R is in the range of C15 to C19.
• the diester when specified, it can include the monoester that is present. The amount of monoester that can be present is the same as in DEQA (1).
• DEQA (2) is the "propyl" ester quaternary ammonium fabric softener active having the formula l,2-di(acyloxy)-3- trimethylammoniopropane chloride, where the acyl is the same as that of FA* disclosed hereinafter.
• Some preferred clear fabric softening compositions of the present invention contain as an essential component from about 2% to about 75%, preferably from about 8% to about 70%, more preferably from about 13% to about 65%, and even more preferably from about 18% to about 45% by weight of the composition, of softener active having the formula:
• each R! in a compound is a C6-C22 hydrocarbyl group, preferably having an
• m is a number from 1 to 3 on the weight average in any mixture of compounds
• each R in a compound is a C ⁇ _2 alkyl or hydroxy alkyl group
• X is a softener compatible anion, preferably methyl sulfate.
• the cis:trans isomer ratio of the fatty acid (of the C18:l component) is at least about 1 :1, preferably about 2:1, more preferably about 3:1, and even more preferably about 4: 1, or higher.
• These preferred compounds, or mixtures of compounds have (a) either a Hunter "L" transmission of at least about 85, typically from about 85 to about 95, preferably from about 90 to about 95, more preferably above about 95, if possible, (b) only low, relatively non-detectable levels, at the conditions of use, of odorous compounds selected from the group consisting of: isopropyl acetate; 2,2'-ethylidenebis(oxy)bis-propane; 1,3,5-trioxane; and/or short chain fatty acid (4-12, especially 6-10, carbon atoms) esters, especially methyl esters; or (c) preferably, both.
• odorous compounds selected from the group consisting of: isopropyl acetate; 2,2'-ethylidenebis(oxy)bis-propane; 1,3,5-trioxane; and/or short chain fatty acid (4-12, especially 6-10, carbon atoms) esters, especially methyl esters; or (c) preferably,
• the Hunter L transmission is measured by (1) mixing the softener active with solvent at a level of about 10% of active, to assure clarity, the preferred solvent being ethoxylated (one mole EO) 2,2,4-trimethyl-l,3-pentanediol and (2) measuring the L color value against distilled water with a Hunter ColorQUEST® colorimeter made by Hunter Associates Laboratory, Reston, Virginia.
• the level of odorant is defined by measuring the level of odorant in a headspace over a sample of the softener active (about 92% active). Chromatograms are generated using about 200 mL of head space sample over about 2.0 grams of sample. The head space sample is trapped on to a solid absorbent and thermally desorbed onto a column directly via cryofocussing at about -100°C. The identifications of materials is based on the peaks in the chromatograms. Some impurities identified are related to the solvent used in the quaternization process, (e.g., ethanol and isopropanol). The ethoxy and methoxy ethers are typically sweet in odor.
• C -Cg methyl esters found in a typical current commercial sample, but not in the typical softener actives of this invention. These esters contribute to the perceived poorer odor of the current commercial samples.
• the level of each odorant in ng/L found in the head space over a preferred active is as follows: Isopropyl acetate - ⁇ 1; 1,3,5-trioxane - 5; 2,2'- ethylidenebis(oxy)-bispropane - ⁇ 1; C 6 methyl ester - ⁇ 1; C 8 Methyl ester - ⁇ 1; and C ]0 Methyl ester - ⁇ 1.
• the acceptable level of each odorant is as follows: isopropyl acetate should be less than about 5, preferably less than about 3, and more preferably less than about 2, nanograms per liter ( ⁇ g/L.); 2,2'-ethylidenebis(oxy)bis-propane should be less than about 200, preferably less than about 100, more preferably less than about 10, and even more preferably less than about 5, nanograms per liter ( ⁇ g/L.); 1,3,5-trioxane should be less than about 50, preferably less than about 20, more preferably less than about 10, and even more preferably less than about 7, nanograms per liter ( ⁇ g/L.); and/or each short chain fatty acid (4-12, especially 6-10, carbon atoms) ester, especially methyl esters should be less than about 4, preferably less than about 3, and more preferably less than about 2, nanograms per liter ( ⁇ g/L.).
• the elimination of color and odor materials can either be accomplished after formation of the compound, or, preferably, by selection of the reactants and the reaction conditions.
• the reactants are selected to have good odor and color.
• the reactants can be cleaned up prior to use.
• the fatty acid reactant can be double or triple distilled to remove color and odor causing bodies and remove short chain fatty acids.
• the color of a triethanolamine reactant if used needs to be controlled to a low color level (e.g. a color reading of about 20 or less on the APHA scale).
• the degree of clean up required is dependent on the level of use and the presence of other ingredients. For example, adding a dye can cover up some colors. However, for clear and/or light colored products, the color must be almost non-detectable. This is especially true for higher levels of active, e.g., from about 2% to about 80%, preferably from about 13% to about 75%, more preferably from about 17% to about 70%, and even more preferably from about 19% to about 65% of the softener active by weight of the composition.
• the odor can be covered up by higher levels of perfume, but at the higher levels of softener active there is a relatively high cost associated with such an approach, especially in terms of having to compromise the odor quality. Odor quality can be further improved by use of ethanol as the quaternization reaction solvent.
• a preferred biodegradable fabric softener compounds comprises quaternary ammonium salt, the quatemized ammonium salt being a quatemized product of condensation between: a)-a fraction of saturated or unsaturated, linear or branched fatty acids, or of derivatives of said acids, said fatty acids or derivatives each possessing a hydrocarbon chain in which the number of atoms is between 5 and 21, and b)-triethanolamine, characterized in that said condensation product has an acid value, measured by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator, of less than about 6.5.
• the acid value is preferably less than or equal to about 5, more preferably less than about 3. Indeed, the lower the AV, the better softness performance is obtained.
• the acid value is determined by titration of the condensation product with a standard KOH solution against a phenolphthalein indicator according to ISO#53402.
• the AV is expressed as mg KOH/g of the condensation product.
• the reactants are present in a molar ratio of fatty acid fraction to triethanolamine of from about 1 :1 to about 2.5:1.
• the optimum softness performance is also affected by the detergent carry-over laundry conditions, and more especially by the presence of the anionic surfactant in the solution in which the softening composition is used. Indeed, the presence of anionic surfactant that is usually carried over from the wash will interact with the softener compound, thereby reducing its performance.
• the mole ratio of fatty acid/ triethanolamine can be critical. Accordingly, where no rinse occurs between the wash cycle and the rinse cycle containing the softening compound, a high amount of anionic surfactant will be carried over in the rinse cycle containing the softening compound. In this instance, it has been found that a fatty acid fraction triethanolamine mole ratio of about 1.4:1 to about 1.8:1 is preferred.
• high amount of anionic surfactant it is meant that the presence of anionic in the rinse cycle at a level such that the molar ratio anionic surfactant/cationic softener compound of the invention is at least about 1/10.
• These fabric softener compounds for use herein are typically mixtures of materials.
• the weight percentages of compounds wherein one (monoester), two (diester), or three (triester) of the triethanolamine hydroxy groups is esterified with a fatty acyl group are as follows: Monoester - from about 12% to about 22%; diester - from about 43% to about 57%; and triester - from about 13% to about 28%.
• These compounds, as formed and used in the formulation of fabric softener compositions typically contain from about 6% to about 20% by weight of solvent, e.g., from about 3% to about 10% of a lower molecular alcohol like ethanol and from about 3% to about 10% of solvent that is more hydrophobic, like hexylene glycol.
• a method of treating fabrics comprises the step of contacting the fabrics in an aqueous medium containing the above softener compounds or softening composition wherein the fatty acid /triethanolamine mole ratio in the softener compound is from about 1.4:1 to about 1.8:1, preferably about 1.5:1 and the aqueous medium comprises a molar ratio of anionic surfactant to said softener compound of the invention of at least about 1:10.
• the method of treating fabrics comprises the step of contacting the fabrics in an aqueous medium containing the softener compound of the invention or softening composition thereof wherein the fatty acid/triethanolamine mole ratio in the softener compound is from about 1.8:1 to about 2:1, preferably about 2.0:1, and most preferably about 1.9, and the aqueous medium comprises a molar ratio of anionic surfactant to said softener compound of the invention of less than about 1 :10.
• the fatty acid fraction and the triethanolamine are present in a molar ratio of from about 1:1 to about 2.5:1.
• Preferred cationic, preferably biodegradable quaternary, ammonium fabric softening compounds can contain the group -(O)CR ⁇ which is derived from animal fats, unsaturated, and polyunsaturated, fatty acids, e.g., oleic acid, and/or partially hydrogenated fatty acids, derived from vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.
• fatty acids are listed in U.S. Pat. No. 5,759,990 at column 4, lines 45-66.
• FA's that can be blended, to form FA's of this invention are as follows: Fattv Acvl Group FA 1 FA 2 FA 3
• FA! is a partially hydrogenated fatty acid prepared from canola oil
• FA 2 is a fatty acid prepared from soy bean oil
• FA 3 is a slightly hydrogenated tallow fatty acid.
• Preferred softener actives contain an effective amount of molecules containing two ester linked hydrophobic groups [R1C(C0)0-], said actives being referred to hereinafter as "DEQA's”, are those that are prepared as a single DEQA from blends of all the different fatty acids that are represented (total fatty acid blend), rather than from blends of mixtures of separate finished DEQA's that are prepared from different portions of the total fatty acid blend.
• the fatty acyl groups are unsaturated, e.g., from about 50% to 100%, preferably from about 55% to about 99%, more preferably from about 60% to about 98%, and that the total level of active containing polyunsaturated fatty acyl groups (TPU) be preferably from 0% to about 30%.
• the cis/trans ratio for the unsaturated fatty acyl groups is usually important, with the cis/trans ratio being from about 1:1 to about 50:1, the minimum being about 1:1, preferably at least about 3:1, and more preferably from about 4:1 to about 20:1. (As used herein, the "percent of softener active" containing a given R! group is the same as the percentage of that same R group is to the total R! groups used to form all of the softener actives.)
• the highly unsaturated materials are also easier to formulate into concentrated premixes that maintain a low viscosity for the neat product composition and are therefore easier to process, e.g., pump, mixing, etc.
• These highly unsaturated materials total level of active containing polyunsaturated fatty acyl groups (TPU) being typically from about 3%> to about 30%, with only the low amount of solvent that normally is associated with such materials, i.e., from about 5% to about 20%, preferably from about 8% to about 25%, more preferably from about 10% to about 20%, weight of the total softener/solvent mixture, are also easier to formulate into concentrated, stable compositions of the present invention, even at ambient temperatures.
• TPU total level of active containing polyunsaturated fatty acyl groups
• substituents R and R* can optionally be substituted with various groups such as alkoxyl or hydroxyl groups, and can be straight, or branched so long as the R groups maintain their basically hydrophobic character.
• a preferred long chain DEQA is the DEQA prepared from sources containing high levels of polyunsaturation, i.e., N,N-di(acyl-oxyethyl)-N,N- methylhydroxyethylammonium methyl sulfate, where the acyl is derived from fatty acids containing sufficient polyunsaturation, e.g., mixtures of tallow fatty acids and soybean fatty acids.
• Another preferred long chain DEQA is the dioleyl (nominally) DEQA, i.e., DEQA in which N,N-di(oleoyl-oxyethyl)-N,N-methylhydroxyethylammonium methyl sulfate is the major ingredient.
• Preferred sources of fatty acids for such DEQAs are vegetable oils, and/or partially hydrogenated vegetable oils, with high contents of unsaturated, e.g., oleoyl groups.
• at least about 30% of the DEQA is in the diester form, and from 0% to about 30% can be DEQA monoester, e.g., there are three R groups and one R! group.
• the percentage of monoester should be as low as possible, preferably no more than about 15%.
• anionic detergent surfactant or detergent builder carry-over conditions some monoester can be preferred.
• the overall ratios of diester "quaternary ammonium active" (quat) to monoester quat are from about
• the di/monoester ratio is preferably about 1.3:1.
• the level of monoester present can be controlled in manufacturing the DEQA by varying the ratio of fatty acid, or fatty acyl source, to triethanolamine.
• the overall ratios of diester quat to triester quat are from about 10:1 to about 1.5:1, preferably from about 5:1 to about 2.8:1.
• the above compounds can be prepared using standard reaction chemistry.
• triethanolamine of the formula N(CH2CH2OH)3 is esterified, preferably at two hydroxyl groups, with an acid chloride of the formula R!C(O)C1, to form an amine which can be made cationic by acidification (one R is H) to be one type of softener, or then quatemized with an alkyl halide, RX, to yield the desired reaction product (wherein R and R* are as defined hereinbefore).
• R and R* are as defined hereinbefore.
• each R! is a hydrocarbyl, or substituted hydrocarbyl, group, preferably, alkyl, monounsaturated alkenyl, and polyunsaturated alkenyl groups, with the softener active containing polyunsaturated alkenyl groups being preferably at least about 3%, more preferably at least about 5%, more preferably at least about 10%, and even more preferably at least about 15%, by weight of the total softener active present; the actives preferably containing mixtures of Rt groups, especially within the individual molecules.
• the DEQAs herein can also contain a low level of fatty acid, which can be from unreacted starting material used to form the DEQA and/or as a by-product of any partial degradation (hydrolysis) of the softener active in the finished composition. It is preferred that the level of free fatty acid be low, preferably below about 15%, more preferably below about 10%, and even more preferably below about 5%, by weight of the softener active.
• the fabric softener actives herein are preferably prepared by a process wherein a chelant, preferably a diethylenetriaminepentaacetate (DTP A) and/or an ethylene diamine- N,N -disuccinate (EDDS) is added to the process.
• a chelant preferably a diethylenetriaminepentaacetate (DTP A) and/or an ethylene diamine- N,N -disuccinate (EDDS) is added to the process.
• Another acceptable chelant is tetrakis- (2-hydroxylpropyl) ethylenediamine (TPED).
• antioxidants are added to the fatty acid immediately after distillation and/or fractionation and/or during the esterification reactions and/or post-added to the finished softener active.
• the resulting softener active has reduced discoloration and malodor associated therewith.
• the total amount of added chelating agent is preferably within the range of from about 10 ppm to about 5,000 ppm, more preferably within the range of from about 100 ppm to about 2500 ppm by weight of the formed softener active.
• the source of triglyceride is preferably selected from the group consisting of animal fats, vegetable oils, partially hydrogenated vegetable oils, and mixtures thereof.
• the vegetable oil or partially hydrogenated vegetable oil is selected from the group consisting of canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated sunflower oil, corn oil, partially hydrogenated corn oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated rice bran oil, and mixtures thereof.
• the source of triglyceride is canola oil, partially hydrogenated canola oil, and mixtures thereof.
• the process can also include the step of adding from about 0.01% to about 2% by weight of the composition of an antioxidant compound to any or all of the steps in the processing of the triglyceride up to, and including, the formation of the fabric softener active.
• Preparation of a fabric softening premix composition comprises preparing a fabric softening active as described above and mixing the fabric softener active, optionally containing a low molecular weight solvent, with a principal solvent having a ClogP, as described hereinafter, of from about -2.0 to about 2.6 thereby forming a fabric softener premix.
• the premix can comprise from about 55% to about 85% by weight of fabric softening active and from about 10% to about 30% by weight of principal solvent.
• the process can also include the step of adding from about 0.01% to about 2% by weight of the composition of an antioxidant compound to any or all of the processing steps.
• compositions can also contain other, usually supplementary, fabric softener active(s), usually in minor amounts, typically from 0% to about 35%, preferably from about 1% to about 20%, more preferably from about 2% to about 10%, said other fabric softener active being selected from:
• each R* is a Cg-C22 > preferably Ci4-C20 > but no more than one being less than about Cj2 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C12-C18 alkyl or alkenyl, and where the Iodine Value (hereinafter referred to as "IV") of a fatty acid containing this R group is from about 70 to about 140, more preferably from about 80 to about 130; and most preferably from about 90 to about 115 (as used herein, the term "Iodine Value” means the Iodine Value of a "parent" fatty acid, or "corresponding" fatty acid, which is used to define a level of unsaturation for an R!
• each R can also preferably be a branched chain C14-C22 alkyl group, preferably a branched chain Cj6-Ci8 group; each R is H or a short chain C j -Cg, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R 2 O)2-4H where each R 2 is a ⁇ .
• A" is a softener compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate, more preferably chloride and methyl sulfate;
• each R, R , and A" have the definitions given above; each R 2 is a ⁇ . alkylene group, preferably an ethylene group; and G is an oxygen atom or an -NR- group;
• R 1 C(O)— NH— R 2 — NH— R3— NH— C(O)— Rl
• R , R 2 are defined as above, and each R 3 is a C ⁇ . alkylene group, preferably an ethylene group;
• reaction product of substantially unsaturated and/or branched chain higher fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said reaction products containing compounds of the formula:
• R, Rl, R 2 , and A" are defined as above;
• R ⁇ and R ⁇ are C1-C4 alkyl or hydroxyalkyl groups, and R and A" are defined as herein above;
• R ⁇ is a C1-C4 alkyl or hydroxyalkyl group, and Rl, R 2 , and A" are as defined above;
• alkylpyridinium salts having the formula:
• R ⁇ is an acyclic aliphatic Cg-C22 hydrocarbon group and A" is an anion; and (12) alkanamide alkylene pyridinium salts having the formula:
• Rl, R 2 and A are defined as herein above; and mixtures thereof.
• Compound (8) examples include the monoalkenyltrimethylammonium salts such as monooleyltrimethylammonium chloride, monocanolatrimethylammonium chloride, and soyatrimethylammonium chloride. Monooleyltrimethylammonium chloride and monocanolatrimethylammonium chloride are preferred. Other examples of Compound (8) are soyatrimethylammonium chloride available from Witco Corporation under the trade name Adogen® 415, erucyltrimethylammonium chloride wherein R!
• Rl is a Ci g-Cj hydrocarbon group
• R ⁇ is a methyl group
• R ⁇ is an ethyl group
• A" is an ethylsulfate anion
• R is a Cj hydrocarbon group
• R ⁇ is a Cj hydrocarbon group
• the additional softener actives herein are preferably those that are highly unsaturated versions of the traditional softener actives, i.e., di-long chain alkyl nitrogen derivatives, normally cationic materials, such as dioleyldimethylammonium chloride and imidazolinium compounds as described hereinafter.
• Examples of more biodegradable fabric softeners can be found in U.S. Pat. Nos. 3,408,361, Mannheimer, issued Oct. 29, 1968; 4,709,045, Kubo et al., issued Nov. 24, 1987; 4,233,451, Pracht et al., issued Nov. 11, 1980; 4,127,489, Pracht et al., issued Nov.
• Examples of Compound (1) are dialkylenedimethylammonium salts such as dicanoladimethylammonium chloride, dicanoladimethylammonium methylsulfate, di(partially hydrogenated soybean, cis/trans ratio of about 4:l)dimethylammonium chloride, dioleyldimethylammonium chloride. Dioleyldimethylammonium chloride and di(canola)dimethylammonium chloride are preferred.
• An example of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Corporation under the trade name Adogen® 472.
• Compound (2) is 1 -methyl- 1-oley lamidoethyl-2- oleylimidazolinium methylsulfate wherein Rl is an acyclic aliphatic C15-C17 hydrocarbon group, R 2 is an ethylene group, G is a NH group, R ⁇ is a methyl group and A" is a methyl sulfate anion, available commercially from the Witco Corporation under the trade name Varisoft® 3690.
• An example of Compound (3) is l-oleylamidoethyl-2-oleylimidazoline wherein R! is an acyclic aliphatic C15-C17 hydrocarbon group, R 2 is an ethylene group, and G is a
• Compound (4) is reaction products of oleic acids with diethylenetriamine in a molecular ratio of about 2:1, said reaction product mixture containing N,N"-dioleoyldiethylenetriamine with the formula:
• R -C(O) is oleoyl group of a commercially available oleic acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021, available from Henkel Corporation, and R 2 and R 3 are divalent ethylene groups.
• Compound (5) is a difatty amidoamine based softener having the formula:
• Compound (6) is reaction products of oleic acids with N-2- hydroxyethylethylenediamine in a molecular ratio of about 2:1, said reaction product mixture containing a compound of the formula:
• R* is derived from oleic acid, and the compound is available from Witco Company.
• An example of Compound (11) is 1 -ethyl- l-(2-hydroxy ethyl)-2- isoheptadecylimidazolinium ethylsulfate wherein R* is a C ⁇ hydrocarbon group, R 2 is an ethylene group, R ⁇ is an ethyl group, and A" is an ethylsulfate anion.
• the anion A which is any softener compatible anion, provides electrical neutrality.
• the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, bromide, or iodide.
• a halide such as chloride, bromide, or iodide.
• other anions can be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate, and the like.
• Chloride and methylsulfate are preferred herein as anion A.
• the anion can also, but less preferably, carry a double charge in which case A " represents half a group.
• the principal solvent is typically used at an effective level up to about 40% by weight, preferably from about 1 % to about 25%, more preferably from about 3 % to about 8 %, by weight of the composition.
• An advantage of the high electrolyte level and/or the phase stabilizers disclosed herein is that lower levels of principal solvents and/or a wider range of principal solvents can be used to provide clarity.
• the ClogP of the principal solvent system as disclosed hereinafter would typically be limited to a range of from about 0.15 to about 0.64 as disclosed in said '443 patent. It is known that higher ClogP compounds, up to about 1 can be used when combined with other solvents as disclosed in copending provisional application Serial No.
• the level of principal solvent can be less and/or the ClogP range that is usable is broadened to include from about -2.0 to about 2.6 , more preferably from about -1.7 to about 1.6, and even more preferably from about -1.0 to about 1.0.
• phase stabilizer as defined hereinafter, in combination with a very low level of principal solvent is sufficient to provide good clarity and/or stability of the composition when the electrolyte is present.
• the level of principal solvent is insufficient to provide the required degree of clarity and/or stability and the addition of the electrolyte and/or the phase stabilizer provides the desired clarity/stability.
• Said electrolyte and/or said phase stabilizer can be used to either make a composition translucent or clear, or can be used to increase the temperature range at which the composition is translucent or clear.
• the principal solvent at the previously indicated levels, in a method in which the said principal solvent is added to a composition that is not translucent, or clear, or which has a temperature where phase instability occurs that is too high, to make the composition translucent or clear, or, when the composition is clear, e.g., at ambient temperature, or down to a specific temperature, to reduce the temperature at which phase instability occurs, preferably by at least about 5°C, more preferably by at least about 10°C.
• the principal solvent is efficient in that it provides the maximum advantage for a given weight of solvent. It is understood that "solvent”, as used herein, refers to the effect of the principal solvent and not to its physical form at a given temperature, since some of the principal solvents are solids at ambient temperature.
• Principal solvents that can be present are selected to minimize solvent odor impact in the composition and to provide a low viscosity to the final composition.
• isopropyl alcohol is flammable and has a strong odor.
• n-Propyl alcohol is more effective, but also has a distinct odor.
• Several butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a principal solvent system to minimize their odor.
• the alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 50°F (about 10°C), more preferably down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C).
• Suitable solvents can be selected based upon their octanol/water partition coefficient (P).
• Octanol/water partition coefficient of a solvent is the ratio between its equilibrium concentration in octanol and in water.
• the partition coefficients of the solvent ingredients of this invention are conveniently given in the form of their logarithm to the base 10, logP.
• the logP of many ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP” program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database.
• the "calculated logP” (ClogP) is determined by the fragment approach of Hansch and Leo (cf, A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p.
• the fragment approach is based on the chemical structure of each ingredient, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding.
• the ClogP values which are the most reliable and widely used estimates for this physicochemical property, are preferably used instead of the experimental logP values in the selection of the principal solvent ingredients which are useful in the present invention.
• Other methods that can be used to compute ClogP include, e.g., Crippen's fragmentation method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan's fragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).
• the principal solvents herein are selected from those having a ClogP of from -2.0 to 2.6, preferably from -1.7 to 1.6, and more preferably from -1.0 to 1.0.,
• the most preferred solvents can be identified by the appearance of the dilute treatment compositions used to treat fabrics. These dilute compositions have dispersions of fabric softener that exhibit a more uni-lamellar appearance than conventional fabric softener compositions. The closer to uni-lamellar the appearance, the better the compositions seem to perform. These compositions provide surprisingly good fabric softening as compared to similar compositions prepared in the conventional way with the same fabric softener active.
• the '443 and PCT disclosures contain reference numbers to the Chemical Abstracts Service Registry numbers (CAS No.) for those compounds that have such a number and the other compounds have a method described, that can be used to prepare the compounds.
• Some inoperable solvents listed in the '443 disclosure can be used in mixtures with operable solvents and/or with the high electrolyte levels and/or phase stabilizers, to make concentrated fabric softener compositions that meet the stability/clarity requirements set forth herein.
• diol solvents that have the same chemical formula can exist as many stereoisomers and/or optical isomers. Each isomer is normally assigned with a different CAS No. For examples, different isomers of 4-methyl-2,3-hexanediol are assigned to at least the following CAS Nos: 146452-51-9; 146452-50-8; 146452-49-5; 146452-48-4; 123807-34-1; 123807-33-0; 123807-32-9; and 123807-31-8.
• each chemical formula is listed with only one CAS No. This disclosure is only for exemplification and is sufficient to allow the practice of the invention. The disclosure is not limiting. Therefore, it is understood that other isomers with other CAS Nos, and their mixtures, are also included.
• a CAS No. represents a molecule which contains some particular isotopes, e.g., deuterium, tritium, carbon-13, etc., it is understood that materials which contain naturally distributed isotopes are also included, and vice versa.
• An effective amount of the principal solvents of this invention is at least greater than about 1%, preferably more than about 3%, more preferably more than about 5% of the composition, when at least about 15% of the softener active is also present.
• Principal solvents preferred for improved clarity at 50 °F are 1,2-hexanediol; 1,2- pentanediol; hexylene glycol; 1,2-butanediol; 1,4-cyclohexanediol; pinacol; 1,5- hexanediol; 1 ,6-hexanediol; and/or 2,4-dimethyl-2,4-pentanediol.
• compositions of this invention contain a relatively high level of electrolyte, e.g., from about 0.5% to about 10%, preferably from about 0.75% to about 3%, and more preferably from about 1% to about 2%, by weight of the composition.
• Increasing the electrolyte level provides at least one benefit selected from (a) lowers the amount of principal solvent having a ClogP of from about 0.15 to about 0.64 or 1, which is required to provide clarity (It can eliminate the need for such a principal solvent completely.); (b) modifies the viscosity/elasticity profile on dilution, to provide lower viscosity and/or elasticity; and (c) modifies the range of ClogP of acceptable principal solvents that will provide clarity/translucency.
• U.S. Pat. No. 5,759,990 incorporated herein by reference, discloses that the principal solvent should have a ClogP of from about 0.15 to about 0.64.
• a high electrolyte level allows the use of principal solvents with a ClogP within ranges having progressively more preferred lower limits of: -2.0; -1.7; -1.0; and 0.15 and having progressively more preferrred upper limits of: 2.6; 2.0; 1.6; 1.0; and 0.64..
• This is a totally unobvious and very important benefit, since many of the solvents that are included in this broader range are more readily available, have lower odors, and can be more effective.
• the existing principal solvents are also more effective with the high electrolyte level, thus allowing one to use less of such principal solvents.
• a ClogP of about 1.6 the use of additional solvents and/or other materials to aid in clarification is highly desirable.
• fabric softener compositions with highly preferred dilution and dispensing behaviors can be identified by evaluating the visco-elastic behavior of a series of water dilutions of the fabric softener composition, or alternatively, by evaluating the visco-elastic properties of the maximum viscosity peak in the dilution series.
• the visco-elastic behavior of the fabric softening composition provides information on the tendency of the fabric softener composition to flow and disperse in a desirable manner when used by the consumer. Viscosity measures the ability of a fluid to flow (ie. dissipate heat) when energy is applied, represented by G", the loss modulus.
• Elasticity which is commonly denoted by the storage modulus G', measures the tendency of the fabric softener composition to be easily deformed as energy is applied.
• G' and G" are generally measured as functions of applied strain or stress.
• G' and G" are measured over a range of energy inputs which encompasses energies likely to be applied in common consumer practices (e.g., machine wash and hand wash processes, pre-dilution steps by hand and machine, machine dispenser use and machine-independent dispenser use). Measuring G' and G" on diluted compositions with maximum viscosity adequately distinguishes fabric softener compositions that have preferred and highly preferred dilution and dispersion behaviors from fabric softener compositions which have less preferred behavior.
• Microscopy shows again that high electrolyte levels allow the creation of formulas at much lower solvent/softener levels that dilute through different microstructures and/or phases which have much lower visco-elasticity. It is believed that microstructures with much lower elasticity, easily yield to slight stresses caused by agitating water in a washing machine, automatic washing machine dispenser, or automatic dispensing device not affixed to the machine agitator such as the Downy ® 'Ball'.
• the electrolytes herein include the usual ones found in opaque, dispersion-type, liquid fabric softener compositions and others that are not normally used in such compositions. It was previously believed that principal solvents were increasing the flexibility of both the fabric softener domain and the water domain and thus promoting the formation of a highly fluid, optically clear, compositions containing a bicontinuous fabric softener active phase. Unexpectedly, it is now found that electrolytes seem to provide the function of increasing the flexibility of the water domain through breaking up the hydrogen bond interactions via complexation with the water molecules. This appears to be the mechanism by which the use of high electrolyte allows the use of lower amounts of principal solvents and increases the range of operable principal solvents.
• Electrolytes function by complexing with water and breaking the hydrogen bond structure of water, it is also believed that the head groups of the fabric softener active and the phase stabilizer must be able to complex with water to increase the steric repulsion that will prevent coalescence of the separate bicontinuous phases of fabric softener actives, thus improving the stability of the typical bicontinuous phase that is present when the fabric softener active is in a clear composition.
• a typical series of anions from soft to hard is: iodide; bromide; isocyanate; orthophosphate; chloride; sulfate; hydroxide; and fluoride.
• the harder anions lower the cloud point of conventional ethoxylated nonionic detergent surfactants more, showing that the harder anions tend to dehydrate the head groups of the ethoxylated surfactants used as phase stabilizers.
• salts that lower the cloud point of a 1% solution of Neodol ® 91-8 to less than about 65°C are less preferred in the fabric softener compositions described herein because the fabric softener compositions made with these salts tend to be cloudy at ambient temperatures.
• Typical approximate cloud points for such a solution are: sodium sulfate - about 54.1°C; potassium sulfate - 64.4°C; ammonium sulfate - about 64.4°C; calcium sulfate (no change - insoluble); magnesium sulfate - about 58.7°C; sodium chloride - about 63- 66.9°C; potassium chloride - about 73.4°C; ammonium chloride - about 73.8°C; calcium chloride - about 73.8°C; and magnesium chloride - about 69.8°C. Potassium acetate provides a cloud point of about about 69.8°C, thus placing the acetate anion somewhere between the chloride and sulfate anions.
• Inorganic salts suitable for reducing dilution viscosity include Mgl 2 , MgBr 2 , MgCl 2 , Mg(NO 3 ) 2 , Mg 3 (PO 4 ) 2 , Mg 2 P 2 O 7 , MgSO 4 , magnesium silicate, Nal, NaBr, NaCl, NaF, Na 3 (PO 4 ), NaSO 3 , Na ⁇ , NajSOj, NaNO 3 , NaIO 3 , Na 3 (PO 4 ), Na 4 P 2 O 7 , sodium silicate, sodium metasilicate, sodium tetrachloroaluminate, sodium tripolyphosphate (STPP), Na ⁇ i , sodium zirconate, CaF 2 , CaCl 2 , CaBr 2 , Cal 2 , CaSO 4 , Ca(NO 3 ) 2 , Ca, KI, KBr, KC1, KF, KNO 3 , KIO 3 , K 2 SO 4 , K 2 SO 3 , K
• potassium alum AlK(SO 4 ) 2 and salts with mixed anions e.g. potassium tetrachloroaluminate and sodium tetrafluoroaluminate.
• Salts incorporating cations from groups Ilia, IVa, Va, Via, Vila, VIII, lb, and lib on the periodic chart with atomic numbers > 13 are also useful in reducing dilution viscosity but less preferred due to their tendency to change oxidation states and thus they can adversely affect the odor or color of the formulation or lower weight efficiency.
• Salts with cations from group la or Ila with atomic numbers > 20 as well as salts with cations from the lactinide or actinide series are useful in reducing dilution viscosity, but less preferred due to lower weight efficiency or toxicity. Mixtures of above salts are also useful.
• Organic salts useful in this invention include, magnesium, sodium, lithium, potassium, zinc, and aluminum salts of the carboxylic acids including formate, acetate, proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g. benzoates, phenolate and substituted benzoates or phenolates, such as phenolate, salicylate, polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate, succinate, benzenedicarboxylate, benzenetricarboxylate.
• carboxylic acids including formate, acetate, proprionate, pelargonate, citrate, gluconate, lactate aromatic acids e.g. benzoates, phenolate and substituted benzoates or phenolates, such as phenolate, salicylate, polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate, succinate, benzenedicarboxylate
• Electrolytes can comprise mixed salts of the above, salts neutralized with mixed cations such as potassium sodium tartrate, partially neutralized salts such as sodium hydrogen tartrate or potassium hydrogen phthalate, and salts comprising one cation with mixed anions.
• inorganic electrolytes are preferred over organic electrolytes for better weight efficiency and lower costs.
• Mixtures of inorganic and organic salts can be used.
• Typical levels of electrolyte in the compositions are less than about 10%.
• Phase stabilizers are highly desirable, and can be essential, to formulating a clear or translucent fabric softener composition (product) with high electrolyte levels. It is believed that clear and translucent products are comprised of surfactants structured in bilayers with an aqueous domain between these bilayers. Oily materials, such as hydrophobic perfumes, can be incorporated within the bilayers between the surfactant tails. In fact, these oily materials can act to stabilize the bilayers if the amount present is not excessive. Water soluble compounds, such as the electrolytes described above tend to stay in the aqueous domain between the bilayers.
• the surfactant structure is normally stabilized by the electrostatic repulsion between the bilayers. Electrostatic repulsion prevents the surfactant bilayers from coalescing and thus splitting into separate phases. When a high level of electrolyte is added to the formula, it is believed that the electrostatic repulsion between bilayers is diminished and this can promote coalescence of the surfactant bilayers. If this coalescence occurs, one, or more, phase stabilizers is added to the formula to provide more stability, e.g., by steric repulsion between the bilayers.
• Typical levels of phase stabilizer in the softening compositions are from an effective amount up to about 15% by weight, preferably from about 0.1% to about 7% by weight, more preferably from about 1% to about 5% by weight of the composition.
• phase stabilizer compounds described herein differ from the principal solvents described hereinbefore by their ability to provide steric repulsion at the interface. These phase stabilizers are not principal solvents as defined herein.
• phase stabilizers useful in the compositions of the present invention are selected surface actives materials commonly comprise of hydrophobic and hydrophilic moieties.
• a preferred hydrophilic moiety is polyalkoxylated group , preferably polyethoxylated group.
• phase stabilizers are nonionic surfactants derived from saturated and/or unsaturated primary, secondary, and/or branched, amine, amide, amine-oxide fatty alcohol, fatty acid, alkyl phenol, and/or alkyl aryl carboxylic acid compounds, each preferably having from about 6 to about 22, more preferably from about 8 to about 18, carbon atoms in a hydrophobic chain, more preferably an alkyl or alkylene chain, wherein at least one active hydrogen of said compounds is ethoxylated with ⁇ 50, preferably ⁇ 30, more preferably from about 5 to about 15, and even more preferably from about 8 to about 12, ethylene oxide moieties to provide an HLB of from about 8 to about 20, preferably from about 10 to about 18, and more preferably from about 11 to about 15.
• Suitable phase stabilizers also include nonionic surfactants with bulky head groups selected from: a. surfactants having the formula
• R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22;
• Y' is selected from the following groups: - O-; -N(A)-; and mixtures thereof; and
• A is selected from the following groups: H; R 1 ; - (R 2 -O) z -H; -(CH 2 ) X CH 3 ; phenyl, or substituted aryl, wherein 0 ⁇ x ⁇ about 3 and z is from about 5 to about 30;
• each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - wherein n is from about 1 to about 4 and/or -[CH(CH 3 )CH 2 ]-; and
• each R 5 is selected from the following groups: -OH; and -O(R 2 O) z -H ;
• each R! is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl; and R 2 is a C5-C31 hydrocarbyl moiety; and each Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an ethoxylated derivative thereof; and each R' is H or a cyclic mono- or poly- saccharide, or alkoxylated derivative thereof; and d. mixtures thereof.
• Suitable phase stabilizers also include surfactant complexes formed by one surfactant ion being neutralized with surfactant ion of opposite charge or an electrolyte ion that is suitable for reducing dilution viscosity and block copolymer surfactants comprising polyethylene oxide moieties and propylene oxide moieties
• phase stabilizers examples include: (1)- Alkyl or alkyl-aryl alkoxylated nonionic surfactants
• Suitable alkyl alkoxylated nonionic surfactants are generally derived from saturated or unsaturated primary, secondary, and branched fatty alcohols, fatty acids, alkyl phenols, or alkyl aryl (e.g., benzoic) carboxylic acid, where the active hydrogen(s) is alkoxylated with ⁇ about 30 alkylene, preferably ethylene, oxide moieties (e.g. ethylene oxide and/or propylene oxide).
• nonionic surfactants for use herein preferably have from about 6 to about 22 carbon atoms on the alkyl or alkenyl chain, and are in either straight chain or branched chain configuration, preferably straight chain configurations having from about 8 to about 18 carbon atoms, with the alkylene oxide being present, preferably at the primary position, in average amounts of ⁇ about 30 moles of alkylene oxide per alkyl chain, more preferably from about 5 to about 15 moles of alkylene oxide, and most preferably from about 8 to about 12 moles of alkylene oxide.
• Preferred materials of this class also have pour points of about 70°F and or do not solidify in these clear formulations.
• alkyl alkoxylated surfactants with straight chains examples include Neodol ® 91-8, 25-9, 1-9, 25-12, 1-9, and 45-13 from Shell, Plurafac ® B-26 and C-17 from BASF, and Brij ® 76 and 35 from ICI Surfactants.
• Examples of branched alkyl alkoxylated surfactants include Tergitol ® 15-S-12, 15-S-15, and 15-S-20 from Union Carbide and Emulphogene ® BC-720 and BC-840 from GAF.
• alkyl-aryl alkoxylated surfactants examples include Igepal ® CO-620 and CO-710, from Rhone Poulenc, Triton ® N-l 11 and N-150 from Union Carbide, Dowfax ® 9N5 from Dow and Lutensol ® AP9 and API 4, from BASF.
• alkyl-aryl alkoxylated surfactants include Igepal ® CO-620 and CO-710, from Rhone Poulenc, Triton ® N-l 11 and N-150 from Union Carbide, Dowfax ® 9N5 from Dow and Lutensol ® AP9 and API 4, from BASF.
• Suitable alkyl alkoxylated nonionic surfactants with amine functionality are generally derived from saturated or unsaturated, primary, secondary, and branched fatty alcohols, fatty acids, fatty methyl esters, alkyl phenol, alkyl benzoates, and alkyl benzoic acids that are converted to amines, amine-oxides, and optionally substituted with a second alkyl or alkyl-aryl hydrocarbon with one or two alkylene oxide chains attached at the amine functionality each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
• alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
• the amine or amine-oxide surfactants for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one hydrocarbon in a straight chain configuration having about 8 to about 18 carbon atoms with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ 50 about moles of alkylene oxide per amine moiety, more preferably from about 5 to about 15 moles of alkylene oxide, and most preferably a single alkylene oxide chain on the amine moiety containing from about 8 to about 12 moles of alkylene oxide per amine moiety.
• Preferred materials of this class also have pour points about 70°F and/or do not solidify in these clear formulations.
• ethoxylated amine surfactants examples include Berol ® 397 and 303 from Rhone Poulenc and Ethomeens ® C/20, C25, T/25, S/20, S/25 and Ethodumeens ® T/20 and T25 from Akzo.
• the compounds of the alkyl or alkyl-aryl alkoxylated surfactants and alkyl or alkyl-aryl amine and amine-oxide alkoxylated have the following general formula:
• each R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain preferably having a length of from about 6 to about 22, more preferably from about 8 to about 18 carbon atoms, and even more preferably from about 8 to about 15 carbon atoms, preferably, linear and with no aryl moiety; wherein each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and/or - [CH(CH 3 )CH 2 ]-; wherein about 1 ⁇ n ⁇ about 3; Y is selected from the following groups: -O-; -N(A) q -; -C(O)O-; - (O -)N(A) q -; -B-R 3 -O-; -B-R 3 -N(A) q -; -B-R 3 -C(O)O-; -
• each alkoxy chain can be replaced by a short chain C M alkyl or acyl group to "cap" the alkoxy chain, z is from about 5 to about 30.
• p is the number of ethoxylate chains, typically one or two, preferably one and m is the number of hydrophobic chains, typically one or two, preferably one and q is a number that completes the structure, usually one.
• the preferred y is 0.
• Suitable alkoxylated and non-alkoxylated phase stabilizers with bulky head groups are generally derived from saturated or unsaturated, primary, secondary, and branched fatty alcohols, fatty acids, alkyl phenol, and alkyl benzoic acids that are derivatized with a carbohydrate group or heterocyclic head group. This structure can then be optionally substituted with more alkyl or alkyl-aryl alkoxylated or non- alkoxylated hydrocarbons.
• the heterocyclic or carbohydrate is alkoxylated with one or more alkylene oxide chains (e.g. ethylene oxide and/or propylene oxide) each having ⁇ about 50, preferably ⁇ about 30, moles per mole of heterocyclic or carbohydrate.
• the hydrocarbon groups on the carbohydrate or heterocyclic surfactant for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one hydrocarbon having from about 8 to about 18 carbon atoms with one or two alkylene oxide chains carbohydrate or heterocyclic moiety with each alkylene oxide chain present in average amounts of ⁇ about 50, preferably ⁇ about 30, moles of carbohydrate or heterocyclic moiety, more preferably from about 5 to about 15 moles of alkylene oxide per alkylene oxide chain, and most preferably between about 8 and about 12 moles of alkylene oxide total per surfactant molecule including alkylene oxide on both the hydrocarbon chain and on the heterocyclic or carbohydrate moiety.
• phase stabilizers in this class are Tween ® 40, 60, and 80 available from ICI Surfactants.
• the compounds of the alkoxylated and non-alkoxylated nonionic surfactants with bulky head groups have the following general formulas:
• R is selected from the group consisting of saturated or unsaturated, primary, secondary or branched chain alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain having a length of from about 6 to about 22;
• Y' is selected from the following groups: - O-; -N(A)-; and mixtures thereof; and
• A is selected from the following groups: H; R 1 ; - (R 2 -O) z -H; -(CH 2 ) X CH 3 ; phenyl, or substituted aryl, wherein 0 ⁇ x ⁇ about 3 and z is from about 5 to about 30;
• each R 2 is selected from the following groups or combinations of the following groups: -(CH 2 ) n - and or -[CH(CH 3 )CH 2 ]-; and
• each R 5 is selected from the following groups: -OH; and -O(R 2 O) z -H ; and
• m is from about 2 to about 4
• each R 5 is selected independently from the following: -H, -OH, -(CH 2 )xCH 3 , -(OR 2 ) z -H, -OR 1 , - OC(O)R ] , and -CH 2 (CH 2 -(OR 2 ) z complicat-H)-CH 2 - (OR 2 ) z .-C(O) R 1 .
• x, R , and R 2 as defined above in section D above and z, z', and z" are all from about 5 ⁇ to ⁇ about 20, more preferably the total number of z + z' + z" is from about 5 ⁇ to ⁇ about 20.
• Another group of surfactants that can be used are polyhydroxy fatty acid amide surfactants of the formula:
• each R 7 is H, C1-C4 hydrocarbyl, C1-C4 alkoxyalkyl, or hydroxyalkyl, e.g., 2- hydroxyethyl, 2-hydroxypropyl, etc., preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl) or methoxyalkyl; and R6 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably eth
• R6 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N- isobutyl, N-2-hydroxyethyl, N-1-methoxypropyl, or N-2-hydroxypropyl.
• R6-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
• Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc. (4)- Alkoxylated cationic quaternary ammonium surfactants
• Alkoxylated cationic quaternary ammonium surfactants suitable for this invention are generally derived from fatty alcohols, fatty acids, fatty methyl esters, alkyl substituted phenols, alkyl substituted benzoic acids, and/or alkyl substituted benzoate esters, and/or fatty acids that are converted to amines which can optionally be further reacted with another long chain alkyl or alkyl-aryl group; this amine compound is then alkoxylated with one or two alkylene oxide chains each having ⁇ about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.
• alkylene oxide moieties e.g. ethylene oxide and/or propylene oxide
• Typical of this class are products obtained from the quaternization of aliphatic saturated or unsaturated, primary, secondary, or branched amines having one or two hydrocarbon chains from about 6 to about 22 carbon atoms alkoxylated with one or two alkylene oxide chains on the amine atom each having less than ⁇ about 50 alkylene oxide moieties.
• the amine hydrocarbons for use herein have from about 6 to about 22 carbon atoms, and are in either straight chain or branched chain configuration, preferably there is one alkyl hydrocarbon group in a straight chain configuration having about 8 to about 18 carbon atoms.
• Suitable quaternary ammonium surfactants are made with one or two alkylene oxide chains attached to the amine moiety, in average amounts of ⁇ about 50 moles of alkylene oxide per alkyl chain, more preferably from about 3 to about 20 moles of alkylene oxide, and most preferably from about 5 to about 12 moles of alkylene oxide per hydrophobic, e.g., alkyl group.
• Preferred materials of this class also have a pour points below about 70°F and/or do not solidify in these clear formulations.
• phase stabilizers of this type include Ethoquad ® 18/25, C/25, and O/25 from Akzo and Variquat ® -66 (soft tallow alkyl bis(polyoxyethyl) ammonium ethyl sulfate with a total of about 16 ethoxy units) from Witco.
• the compounds of the ammonium alkoxylated cationic surfactants have the following general formula:
• R and R 2 are as defined previously in section D above;
• Surfactant complexes are considered to be surfactant ions neutralized with a surfactant ion of opposite charge or a surfactant neutralized with an electrolyte that is suitable for reducing dilution viscosity, an ammonium salt, or a polycationic ammonium salt.
• a surfactant complex is formed by surfactants of opposite charge, it is preferable that the surfactants have distinctly different chain lengths e.g. a long-chain surfactant complexed with a short-chain surfactant to enhance the solubility of the complex and it is more preferable that the that the long chain surfactant be the amine or ammonium containing surfactant.
• Long chain surfactants are defined as containing alkyl chains with from about 6 to about 22 carbon atoms. These alkyl chains can optionally contain a phenyl or substituted phenyl group or alkylene oxide moieties between the chain and the head group. Short chain surfactants are defined as containing alkyl chains with less than 6 carbons and optionally these alkyl chains could contain a phenyl or substituted phenyl group or alkylene oxide moieties between the alkyl chain and the head group.
• Suitable surfactant complexes include mixtures of Armeen ® APA-10 and calcium xylene sulfonate, Armeen APA-10 and magnesium chloride, lauryl carboxylate and triethanol amine, linear alkyl benzene sulfonate and C 5 -dimethyl amine, or alkyl ethoxylated sulfate and tetrakis N,N,N'N' (2- hydroxylpropyl) ethylenediamine.
• long-chain surfactants for making complexes have the following general formula:
• R 1 is as hereinbefore from section D above and Y 2 can be chosen from the following structures: -N(A) 2 ; -C(O)N(A) 2 ; -(O ⁇ -)N(A) 2 ; -B-R 3 -N(A) 2 ; -B-R 3 - C(O)N(A) 2 ; -B-R J -N(->O)(A) 2 ; -CO 2 " ; -SO 3 "2 ; -OSO 3 "2 ; -O(R 2 O) x CO 2 " ; -O(RO) X SO 3 ' and -O(R 2 O) x OSO 3 "2 ; with B and R 3 as is hereinbefore section D above and 0 ⁇ x ⁇ 4 .
• short-chain surfactants for making complexes have the following general formula:
• R 4 -Y 2 wherein R 1 , R 3 , B, and Y 2 are as hereinbefore and R 4 can be chosen from the following: -(CH 2 ) y CH 3 ; -(CH 2 ) y -phenyl or -(CH 2 ) y -substituted phenyl with 0 ⁇ y ⁇ 6
• Suitable polymers include a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene and/or propylene terephthalate and polyethylene oxide terephthalate at a preferred molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from about 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymer is in the range of from about 5,000 to about 55,000.
• Another preferred polymer is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
• this polymer include the commercially available materials Zelcon® 4780 (from DuPont) and Milease® T (from ICI).
• Highly preferred polymers have the generic formula: X-(OCH 2 CH2)n-[O-C(O)-R 1 -C(O)-O-R ) u - [O-C ⁇ -R 1 -C(O)-O)-(CH 2 CH 2 O) n -X ( 1 ) in which X can be any suitable capping group, with each X being selected from the group consisting of H, and alkyl or acyl groups containing from about 1 to about 4 carbon atoms, preferably methyl, n is selected for water solubility and generally is from about 6 to about 113, preferably from about 20 to about 50, and u is critical to formulation in a liquid composition having a relatively high ionic strength.
• the R! moieties are essentially 1,4-phenylene moieties.
• the term "the R! moieties are essentially 1,4-phenylene moieties” refers to compounds where the R! moieties consist entirely of 1 ,4-phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
• Arylene and alkarylene moieties which can be partially substituted for 1 ,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof.
• Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1 ,2-propylene, 1 ,4-butylene, 1,5-pentylene, 1 ,6-hexamethylene, 1 ,7-heptamethylene,
• the degree of partial substitution with moieties other than 1,4-phenylene should be such that the desired properties of the compound are not adversely affected to any great extent.
• the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
• compounds where the Rl comprise from about 50% to about 100% 1,4-phenylene moieties (from 0 to about 50% moieties other than 1 ,4-phenylene) are adequate.
• the R! moieties consist entirely of (i.e., comprise 100%) 1 ,4-phenylene moieties, i.e., each R ⁇ moiety is 1 ,4-phenylene.
• suitable ethylene or substituted ethylene moieties include ethylene, 1 ,2-propylene, 1,2-butylene, 1 ,2-hexylene, 3-methoxy-l,2-propylene and mixtures thereof.
• the R 2 moieties are essentially ethylene moieties, 1,2-propylene moieties or mixture thereof.
• inclusion of a greater percentage of 1 ,2-propylene moieties tends to improve the water solubility of the compounds.
• the use of 1 ,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the polymer in the liquid fabric softener compositions.
• each n is at least about 6, and preferably is at least about 10.
• the value for each n usually ranges from about 12 to about 113. Typically, the value for each n is in the range of from about 12 to about 43.
• copolymer can optionally contain propylene oxide in an amount up to about 15% by weight.
• copolymer surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.
• Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described hereinbefore include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound.
• a particularly preferred copolymer contains from about 40% to about 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend comprising about 75%, by weight of the blend, of a reverse block copolymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25%, by weight of the blend, of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane.
• Suitable for use as copolymer are those having relatively high hydrophilic- lipophilic balance (HLB).
• polymers useful herein include the polyethylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, have a melting point within the range of from about 30°C to about 100°C, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol with the requisite number of moles of ethylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol.
• block copolymers include the polyalkylene oxide polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side chains, and having the general formula:
• R 1 (CH 3 )2SiO— [(CH 3 )2SiO]a— [(CH 3 )(R 1 )SiO]lr-Si(CH3)2— R 1 wherein a + b are from about 1 to about 50, preferably from about 3 to about 30 , more preferably from about 10 to about 25, and each R is the same or different and is selected from the group consisting of methyl and a poly(ethyleneoxide/propyleneoxide) copolymer group having the general formula:
• each R being a poly(ethyleneoxy/propyleneoxy) copolymer group, and wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side groups) has a value of from 1 to about 100, preferably from about 6 to about 100; total d is from 0 to about 14, preferably from 0 to about 3; and more preferably d is 0; total c+d has a value of from about 5 to about 150, preferably from about 9 to about 100 and each R 2 is the same or different and is selected from the group consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably hydrogen and methyl group.
• Each polyalkylene oxide polysiloxane has at least one Rl group being a poly(ethyleneoxide/propyleneoxide) copolymer group.
• Nonlimiting examples of this type of surfactants are the Silwet® surfactants which are available OSi Specialties, Inc., Danbury, Connecticut.
• Representative Silwet surfactants which contain only ethyleneoxy (C2H4O) groups are as follows.
• Nonlimiting examples of surfactants which contain both ethyleneoxy (C2 H4 O) and propyleneoxy (C3 Hg O) groups are as follows.
• the molecular weight of the polyalkyleneoxy group (R!) is less than or equal to about 10,000.
• the molecular weight of the polyalkyleneoxy group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000.
• the values of c and d can be those numbers which provide molecular weights within these ranges.
• the number of ethyleneoxy units (-C2H4O) in the polyether chain (Rl) must be sufficient to render the polyalkylene oxide polysiloxane water dispersible or water soluble. If propyleneoxy groups are present in the poly alky lenoxy chain, they can be distributed randomly in the chain or exist as blocks.
• Silwet surfactants which contain only propyleneoxy groups without ethyleneoxy groups are not preferred.
• Preferred Silwet surfactants are L-7600, L-7602, L-7604, L-7605, L-7657, and mixtures thereof.
• polyalkylene oxide polysiloxane surfactants can also provide other benefits, such as antistatic benefits, lubricity and softness to fabrics.
• polyalkylene oxide polysiloxanes of the present invention can be prepared according to the procedure set forth in U.S. Pat. No. 3,299,112, incorporated herein by reference.
• polyalkylene oxide polysiloxanes of the surfactant blend of the present invention are readily prepared by an addition reaction between a hydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen) and an alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked polyalkylene oxide).
• a hydrosiloxane i.e., a siloxane containing silicon-bonded hydrogen
• an alkenyl ether e.g., a vinyl, allyl, or methallyl ether
• reaction conditions employed in addition reactions of this type are well known in the art and in general involve heating the reactants (e.g., at a temperature of from about 85° C. to 110° C.) in the presence of a platinum catalyst (e.g., chloroplatinic acid) and a solvent (e.g., toluene).
• a platinum catalyst e.g., chloroplatinic acid
• a solvent e.g., toluene
• Suitable surfactants have the formula:
• R is C 7 . 2] linear alkyl, C 7 . 21 branched alkyl, C 7 . 21 linear alkenyl, C 7.21 branched alkenyl, and mixtures thereof.
• R is C 8 . 18 linear alkyl or alkenyl.
• R 1 is -CH 2 -CH2-
• R 2 is C 3 -C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably R 2 is -CH(CH 3 )-CH 2 -.
• Surfactants which comprise a mixture of Rl and R2 units preferably comprise from about 4 to about 12 -CH 2 -CH 2 - units in combination with from about 1 to about 4 -CH(CH 3 )-CH 2 - units.
• the units may be alternating or grouped together in any combination suitable to the formulator.
• the ratio of R 1 units to R 2 units is from about 4 : 1 to about 8 : 1.
• an R 2 unit i.e. -C(CH 3 )H-CH 2 -
• R 3 is hydrogen, C r C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.
• R 4 is hydrogen, C,-C 4 linear alkyl, C 3 -C 4 branched alkyl, and mixtures thereof; preferably hydrogen.
• index m is equal to 2
• index n must be equal to 0 and the R4 unit is absent.
• the index m is 1 or 2, the index n is 0 or 1, provided that m + n equals 2; preferably m is equal to 1 and n is equal to 1, resulting in one - [(R'O) x (R 2 O) y R 3 ] unit and R4 being present on the nitrogen.
• the index x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10.
• the index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4.
• Preferably all the alkyleneoxy units are ethyleneoxy units.
• ethoxylated alkyl amide surfactants are Rewopal ® C 6 from Witco, Amidox ® C5 from Stepan, and Ethomid ® O / 17 and Ethomid ® HT / 60 from Akzo.; and (8).- Mixtures thereof.
• compositions In terms of principal solvent reduction, with the invention compositions, a reduction of at least 30% can be made without impairing the performance of the composition compared to compositions without the phase stabilizers hereinbefore described. Using a preferred sub-class, a reduction of more than 50% is possible.
• phase stabilizers provide an improved range of temperatures at which the compositions are clear and stable. They also allow more electrolyte to be used without instability. Finally, they can reduce the amount of principal solvent needed to achieve clarity and/or stability.
• the preferred phase stabilizers are alkoxylated alkyls, alkoxylated acyl amides, alkoxylated alkyl amines or alkoxylated quaternary alkyl ammonium salts, surfactant complexes, and mixtures thereof.
• the various stabilizers have different advantages. For example, alkoxylated cationic materials or cationic surfactant complexes improve softness and provide enhanced wrinkle release benefits.
• the softener active compound is di(acyloxyethyl)(2- hydroxyethyl)methyl ammonium methyl sulfate, where the acyl group is derived from partially hydrogenated canola fatty acid, it has been found that the preferred level of stabilizer for optimum clarity and stability increases with increasing level of principal solvent and optional perfume, and decreases with increasing levels of softener active.
• the present invention can contain any softener compatible perfume. Suitable perfumes are disclosed in U.S. Pat. Nos. 5,500,138 and 5,652,206, Bacon et al., issued March 19, 1996 and July 29, 1997 respectively, said patents being incorporated herein by reference.
• perfume includes fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances.
• natural i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants
• artificial i.e., a mixture of different nature oils or oil constituents
• synthetic i.e., synthetically produced
• perfumes are complex mixtures of a plurality of organic compounds.
• perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, those materials disclosed in said patents.
• the perfumes useful in the present invention compositions are preferably substantially free of halogenated materials and nitromusks.
• Suitable solvents, diluents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylene glycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc.
• the amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
• Perfume can be present at a level of from 0% to about 15%, preferably from about 0.1% to about 8%, and more preferably from about 0.2% to about 5%, by weight of the finished composition.
• Fabric softener compositions of the present invention provide improved fabric perfume deposition.
• compositions of the present invention can optionally include a principal solvent extender to enhance stability and clarity of the formulations and in certain instances provide increased softness benefits.
• the solvent extender is typically incorporated in amounts ranging from about 0.05% to about 10%, more preferably from about 0.5% to about 5% and most preferably from about 1% to about 4% by weight of the composition.
• the principal solvent extender may include a range of materials with proviso that the material provide stability and clarity to a compositions having reduced principal solvent levels and typically reduced perfume or fragrance levels.
• Such materials typically include hydrophobic materials such as polar and non-polar oils, and more hydrophilic materials like hydrotropes and electrolytes as disclosed above, e.g. electrolytes of groups IIB, III and IV of the periodic table in particular electrolytes of groups IIB and IIIB such as aluminum, zinc, tin chloride electrolytes, sodium EDTA, sodium DPT A, and other electrolytes used as metal chelators.
• Polar hydrophobic oils may be selected from emollients such as fatty esters, e.g. methyl oleates, Wickenols ® , derivatives of myristic acid such as isopropyl myristate, and triglycerides such as canola oil; free fatty acids such as those derived from canola oils, fatty alcohols such as oleyl alcohol, bulky esters such as benzyl benzoate and benzyl salicylate, diethyl or dibutyl phthalate; bulky alcohols or diols; and perfume oils particularly low-odor perfume oils such as linalool; mono or poly sorbitan esters; and mixtures thereof.
• emollients such as fatty esters, e.g. methyl oleates, Wickenols ® , derivatives of myristic acid such as isopropyl myristate, and triglycerides such as canola oil
• free fatty acids
• Non-polar hydrophobic oils may be selected from petroleum derived oils such as hexane, decane, penta decane, dodecane, isopropyl citrate and perfume bulky oils such as limonene, and mixtures thereof.
• the free fatty acids such as partially hardened canola oil may provide increased softness benefits.
• hydrophobic oils include the polar hydrophobic oils.
• polar hydrophobic oils which have a freezing point, as defined by a 20% solution of the extender in 2,2,4-trimethyl-l,3-pentanediol, of less than about 22°C and more preferably less than about 20°C.
• Preferred oils in this class include methyl oleate, benzyl benzoate and canola oil.
• Suitable hydrotropes include sulfonate electrolytes particularly alkali metal sulfonates and carboxylic acid derivatives such as isopropyl citrate. In particular, sodium and calcium cumene sulfonates and sodium toluene sulfonate.
• Alternative hydrotropes include benzoic acid and its derivatives, electrolytes of benzoic acid and its derivatives. (c). Cationic Charge Boosters
• Cationic charge boosters may be added to the rinse-added fabric softening compositions of the present invention if needed. Some of the charge boosters serve other functions as described hereinbefore.
• ethanol is used to prepare many of the below listed ingredients and is therefore a source of solvent into the final product formulation.
• the formulator is not limited to ethanol, but instead can add other solvents inter alia hexyleneglycol to aid in formulation of the final composition.
• a preferred composition of the present invention comprises at least about 0.2%, preferably from about 0.2% to about 10%, more preferably from about 0.2% to about 5% by weight, of a cationic charge booster having the formula:
• Rl, R 2 , R 3 , and R ⁇ are each independently C1-C22 alkyl, C3-C22 alkenyl, R ⁇ -Q- (CH2) m -, wherein R ⁇ is C1-C22 alkyl, and mixtures thereof, m is from 1 to about 6; X is an anion.
• T is Cg-C22 alkyl, Cg-C22 alkenyl, and mixtures thereof, more preferably Cu-Cjg alkyl, Cy-C ⁇ g alkenyl, and mixtures thereof;
• R 2 , R 3 , and R ⁇ are each preferably C1-C4 alkyl, more preferably each R 2 , R 3 , and R ⁇ are methyl.
• Rl may similarly choose Rl to be a R5-Q-(CH2) m - moiety wherein R ⁇ is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl or alkenyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
• R ⁇ is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl or alkenyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of t
• An example of a fabric softener cationic booster comprising a R ⁇ -Q-(CH2) m - moiety has the formula: wherein R*-Q- is an oleoyl units and m is equal to 2.
• X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
• a strong acid for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
• a preferred composition according to the present invention contains at least about 0.2%, preferably from about 0.2% to about 5%, more preferably from about 0.2% to about 2% by weight, of one or more polyvinyl amines having the formula
• y is from about 3 to about 10,000, preferably from about 10 to about 5,000, more preferably from about 20 to about 500.
• Polyvinyl amines suitable for use in the present invention are available from BASF.
• one or more of the polyvinyl amine backbone -NH2 unit hydrogens can be substituted by an alkyleneoxy unit having the formula:
• R* is C2-C4 alkylene, R 2 is hydrogen, C1-C4 alkyl, and mixtures thereof; x is from
• the polyvinyl amine is reacted first with a substrate which places a 2-propyleneoxy unit directly on the nitrogen followed by reaction of one or more moles of ethylene oxide to form a unit having the general formula:
• x has the value of from 1 to about 50. Substitutions such as the above are represented by the abbreviated formula PO-EO x -. However, more than one propyleneoxy unit can be incorporated into the alkyleneoxy substituent.
• Polyvinyl amines are especially preferred for use as cationic charge booster in liquid fabric softening compositions since the greater number of amine moieties per unit weight provides substantial charge density.
• the cationic charge is generated in situ and the level of cationic charge can be adjusted by the formulator.
• a preferred composition of the present invention comprises at least about 0.2%, preferably from about 0.2% to about 10%, more preferably from about 0.2% to about 5% by weight, of a polyalkyleneimine charge booster having the formula:
• the compounds of the present invention comprise polyamines having a ratio of m
• n that is at least 1:1 but may include linear polymers (n equal to 0) as well as a range as high as 10:1, preferably the ratio is 2:1.
• the ratio of m:n is 2:1
• the ratio of primary: secondary :tertary amine moieties, that is the ratio of -R H2, -RNH, and -RN moieties is 1:2:1.
• R units are C2-C alkylene, C -Cg alkyl substituted alkylene, and mixtures thereof, preferably ethylene, 1,2-propylene, 1,3-propylene, and mixtures thereof, more preferably ethylene.
• R units serve to connect the amine nitrogens of the backbone.
• one or more of the polyvinyl amine backbone -NH2 unit hydrogens can be substituted by an alkyleneoxy unit having the formula:
• R ⁇ is C2-C4 alkylene
• R 2 is hydrogen, C1-C4 alkyl, and mixtures thereof
• x is from
• the polyvinyl amine is reacted first with a substrate which places a 2-propyleneoxy unit directly on the nitrogen followed by reaction of one or more moles of ethylene oxide to form a unit having the general formula:
• x has the value of from 1 to about 50. Substitutions such as the above are represented by the abbreviated formula PO-EO x -. However, more than one propyleneoxy unit can be incorporated into the alkyleneoxy substituent.
• the preferred polyamine cationic charge boosters suitable for use in rinse-added fabric softener compositions comprise backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms.
• the use of two and three carbon spacers as R moieties between nitrogen atoms in the backbone is advantageous for controlling the charge booster properties of the molecules.
• More preferred embodiments of the present invention comprise less than 25% moieties having more than 3 carbon atoms.
• Yet more preferred backbones comprise less than 10% moieties having more than 3 carbon atoms.
• Most preferred backbones comprise 100% ethylene moieties.
• the cationic charge boosting polyamines of the present invention comprise homogeneous or non-homogeneous polyamine backbones, preferably homogeneous backbones.
• homogeneous polyamine backbone is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone that are present due to an artifact of the chosen method of chemical synthesis.
• ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator” would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention.
• non-homogeneous polymer backbone refers to polyamine backbones that are a composite of one or more alkylene or substituted alkylene moieties, for example, ethylene and 1 ,2-propylene units taken together as R units
• PAA polyalkyleneamine
• PAF polyalkyleneimines
• PEA's polyethyleneamine
• PEI's polyethyleneimines
• a common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
• TETA triethylenetetramine
• TEPA tetraethylenepentamine
• the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
• the PEI's which comprise the preferred backbones of the charge boosters of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• Specific methods for preparing PEI's are disclosed in U.S. 2,182,306, Ulrich et al., issued December 5, 1939; U.S. 3,033,746, Mayle et al, issued May 8, 1962; U.S. 2,208,095, Esselmann et al, issued July 16, 1940; U.S. 2,806,839, Crowther, issued September 17, 1957; and U.
• the present invention also includes the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.
• a preferred composition of the present invention comprises at least about 0.2%, preferably from about 0.2% to about 10%, more preferably from about 0.2% to about 5% by weight, of a cationic charge booster having the formula:
• R is substituted or unsubstituted C2-C12 alkylene, substituted or unsubstituted C2- Cj2 hydroxyalkylene; each R is independently C1-C4 alkyl, each R 2 is independently C ⁇ - C22 alkyl, C3-C22 alkenyl, R 5 -Q-(CH2) m -, wherein R 5 is C1-C22 alkyl, C3-C22 alkenyl, and mixtures thereof; m is from 1 to about 6; Q is a carbonyl unit as defined hereinabove; and mixtures thereof; X is an anion.
• R is ethylene; Rl is methyl or ethyl, more preferably methyl; at least one R 2 is preferably C1-C4 alkyl, more preferably methyl. Preferably at least one R 2 is C ⁇ ⁇ - C22 alkyl, C ⁇ 1-C22 alkenyl, and mixtures thereof.
• the formulator may similarly choose R 2 to be a R ⁇ -Q-(CH2) m - moiety wherein R ⁇ is an alkyl moiety having from 1 to 22 carbon atoms, preferably the alkyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof.
• R ⁇ is an alkyl moiety having from 1 to 22 carbon atoms, preferably the alkyl moiety when taken together with the Q unit is an acyl unit derived preferably derived from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated l
• An example of a fabric softener cationic booster comprising a R5-Q-(CH2) m - moiety has the formula: ein R is methyl, one R 2 units is methyl and the other R 2 unit is R5-Q-(CH2) m -wherein R ⁇ -
• Q- is an oleoyl unit and m is equal to 2.
• X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
• a strong acid for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate.
• Composition herein can contain from about 0.001% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.1% to about 2%, of cationic polymer, typically having a molecular weight of from about 500 to about 1,000,000, preferably from about 1,000 to about 500,000, more preferably from about 1,000 to about 250,000, and even more preferably from about 2,000 to about 100,000 and a charge density of at least about 0.01 meq/gm., preferably from about 0.1 to about 8 meq/gm., more preferably from about 0.5 to about 7, and even more preferably from about 2 to about 6.
• cationic polymer typically having a molecular weight of from about 500 to about 1,000,000, preferably from about 1,000 to about 500,000, more preferably from about 1,000 to about 250,000, and even more preferably from about 2,000 to about 100,000 and a charge density of at least about 0.01 meq/gm., preferably from about 0.1 to about 8 meq/gm., more preferably from about 0.5 to about 7, and even
• the cationic polymers of the present invention can be amine salts or quaternary ammonium salts. Preferred are quaternary ammonium salts. They include cationic derivatives of natural polymers such as some polysaccharide, gums, starch and certain cationic synthetic polymers such as polymers and copolymers of cationic vinyl pyridine or vinyl pyridinium halides. Preferably the polymers are water soluble, for instance to the extent of at least 0.5% by weight at 20°C. Preferably they have molecular weights of from about 600 to about 1,000,000, more preferably from about 600 to about 500,000, even more preferably from about 800 to about 300,000, and especially from about 1000 to 10,000.
• the cationic polymers should have a charge density of at least about 0.01 meq/gm., preferably from about 0.1 to about 8 meq/gm., more preferably from about 0.5 to about 7, and even more preferably from about 2 to about 6.
• Suitable desirable cationic polymers are disclosed in "CTFA International Cosmetic Ingredient Dictionary, Fourth Edition, J. M. Nikitakis, et al, Editors, published by the Cosmetic, Toiletry, and Fragrance Association, 1991, incorporated herein by reference. The list includes the following:
• guar and locust bean gums which are galactomannam gums are available commercially, and are preferred.
• guar gums are marketed under Trade Names CSAA M/200, CSA 200/50 by Meyhall and Stein-Hall, and hydroxyalkylated guar gums are available from the same suppliers.
• Other polysaccharide gums commercially available include: Xanthan Gum; Ghatti Gum; Tamarind Gum; Gum Arabic; and Agar.
• Cationic guar gums and methods for making them are disclosed in British Pat. No. 1,136,842 and U.S. Pat. No. 4,031,307. Preferably they have a D.S. of from 0.1 to about 0.5.
• An effective cationic guar gum is Jaguar C-13S (Trade Name—Meyhall).
• Cationic guar gums are a highly preferred group of cationic polymers in compositions according to the invention and act both as scavengers for residual anionic surfactant and also add to the softening effect of cationic textile softeners even when used in baths containing little or no residual anionic surfactant.
• the other polysaccharide-based gums can be quatemized similarly and act substantially in the same way with varying degrees of effectiveness.
• Suitable starches and derivatives are the natural starches such as those obtained from maize, wheat, barley etc., and from roots such as potato, tapioca etc., and dextrins, particularly the pyrodextrins such as British gum and white dextrin.
• Some very effective individual cationic polymers are the following: Polyvinyl pyridine, molecular weight about 40,000, with about 60% of the available pyridine nitrogens quatemized.; Copolymer of 70/30 molar proportions of vinyl pyridine/styrene, molecular weight about 43,000, with about 45% of the available pyridine nitrogens quatemized as above; Copolymers of 60/40 molar proportions of vinyl pyridine/acrylamide, with about 35% of the available pyridine nitrogens quatemized as above. Copolymers of 77/23 and 57/43 molar proportions of vinyl pyridine/methyl methacrylate, molecular weight about 43,000, with about 97% of the available pyridine nitrogens quatemized as above.
• cationic polymers are effective in the compositions at very low concentrations for instance from 0.001% by weight to 0.2% especially from about 0.02% to 0.1%. In some instances the effectiveness seems to fall off, when the content exceeds some optimum level, such as for polyvinyl pyridine and its styrene copolymer about 0.05%.
• Some other effective cationic polymers are: Copolymer of vinyl pyridine and N- vinyl pyrrolidone (63/37) with about 40% of the available pyridine nitrogens quatemized.; Copolymer of vinyl pyridine and acrylonitrile (60/40), quatemized as above.; Copolymer of N,N-dimethyl amino ethyl methacrylate and styrene (55/45) quatemized as above at about 75% of the available amino nitrogen atoms. Eudragit E (Trade Name of Rohm GmbH) quatemized as above at about 75% of the available amino nitrogens.
• Eudragit E is believed to be copolymer of N,N-dialkyl amino alkyl methacrylate and a neutral acrylic acid ester, and to have molecular weight about 100,000 to 1,000,000.; Copolymer of N- vinyl pyrrolidone and N,N-diethyl amino methyl methacrylate (40/50), quatemized at about 50% of the available amino nitrogens.; These cationic polymers can be prepared in a known manner by quatemising the basic polymers.
• cationic polymeric salts are quatemized polyethyleneimines. These have at least 10 repeating units, some or all being quatemized. Commercial examples of polymers of this class are also sold under the generic Trade Name Alcostat by Allied Colloids.
• Each polyamine nitrogen whether primary, secondary or tertiary, is further defined as being a member of one of three general classes; simple substituted, quatemized or oxidized.
• the polymers are made neutral by water soluble anions such as chlorine (Cl"), bromin (Br), iodine (I") or any other negatively charged radical such as sulfate (SO4 2 ”) and methosulfate (CH3SO3-).
• water soluble anions such as chlorine (Cl"), bromin (Br), iodine (I") or any other negatively charged radical such as sulfate (SO4 2 ”) and methosulfate (CH3SO3-).
• modified polyamine cationic polymers of the present invention comprising PEI's comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H.
• Suitable polyamine cationic polymers comprise this molecule which is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides and/or some backbone amine units are quatemized, e.g. with methyl groups.
• compositions herein can also optionally contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.001% to about 1% by weight of such optical brighteners.
• hydrophilic optical brighteners useful in the present invention are those described in said U. S. Pat. No. 5,759,990 at column 21, lines 15-60. (e). Mono-Alkyl Cationic Quaternary Ammonium Compound
• the mono-long chain alkyl cationic quaternary ammonium compound When the mono-long chain alkyl cationic quaternary ammonium compound is present, it is typically present at a level of from about 2% to about 25%, preferably from about 3% to about 17%, more preferably from about 4% to about 15%, and even more preferably from about 5% to about 13% by weight of the composition, the total mono- alkyl cationic quaternary ammonium compound being at least at an effective level to improve softening in the presence of anionic surfactant.
• Such mono-alkyl cationic quaternary ammonium compounds useful in the present invention are, preferably, quaternary ammonium salts of the general formula:
• R4 is Cg-C22 alkyl or alkenyl group, preferably C ⁇ Q- ig alkyl or alkenyl group; more preferably C ⁇ 0-C14 or C ⁇ -Cjg alkyl or alkenyl group; each R5 is a Ci -Cg alkyl or substituted alkyl group (e.g., hydroxy alkyl), preferably C ⁇ -
• C3 alkyl group e.g., methyl (most preferred), ethyl, propyl, and the like, a benzyl group, hydrogen, a polyethoxylated chain with from about 2 to about 20 oxyethylene units, preferably from about 2.5 to about 13 oxyethylene units, more preferably from about 3 to about 10 oxyethylene units, and mixtures thereof; and A" is as defined hereinbefore for (Formula (I)).
• monolauryl trimethyl ammonium chloride and monotallow trimethyl ammonium chloride available from Witco under the trade name Varisoft® 471 and monooleyl trimethyl ammonium chloride available from Witco under the tradename Varisoft® 417.
• the R4 group can also be attached to the cationic nitrogen atom through a group containing one, or more, ester, amide, ether, amine, etc., linking groups.
• Such linking groups are preferably within from about one to about three carbon atoms of the nitrogen atom.
• Mono-alkyl cationic quaternary ammonium compounds also include C -C22 alkyl choline esters.
• the preferred compounds of this type have the formula:
• Highly preferred compounds include C12-C14 coco choline ester and C ⁇ -Cj tallow choline ester.
• Suitable mono-long chain materials correspond to the preferred biodegradable softener actives disclosed above, where only one Rl group is present in the molecule.
• the R group or YRI group is replaced normally by an R group.
• the ratio of fabric softener active to single long chain compound is typically from about 100:1 to about 2:1, preferably from about 50:1 to about 5:1, more preferably from about 13:1 to about 8:1. Under high detergent carry-over conditions, the ratio is preferably from about 5 : 1 to about 7:1.
• the single long chain compound is present at a level of about 10 ppm to about 25 ppm in the rinse, (f).
• Stabilizers can be present in the compositions of the present invention.
• the term "stabilizer,” as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.035% to about 0.1% for antioxidants, and, preferably, from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions. Antioxidants and reductive agent stabilizers are especially critical for unscented or low scent products (no or low perfume).
• antioxidants examples include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox® S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), propyl gallate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox®-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox® TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox® GT-l/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long chain esters (C ⁇ -C j ) of gallic acid, e
• Suitable soil release agents are disclosed in the U.S. Pat. No. 5,759,990 at column 23, line 53 through column 25, line 41.
• the addition of the soil release agent can occur in combination with the premix, in combination with the acid/water seat, before or after electrolyte addition, or after the final composition is made.
• the softening composition prepared by the process of the present invention herein can contain from 0% to about 10%, preferably from 0.2% to about 5%, of a soil release agent.
• a soil release agent is a polymer.
• Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like.
• a preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 5,000 to about 55,000.
• Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
• this polymer include the commercially available materials Zelcon 4780® (from Dupont) and Milease T® (from ICI). These soil release agents can also act as a scum dispersant. (h).
• Bactericides Bactericides
• compositions and processes herein can optionally employ one or more copper and/or nickel chelating agents ("chelators").
• chelators can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined.
• the whiteness and/or brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved.
• the chelating agents are typically used in the present rinse process at levels from about 2 ppm to about 25 ppm, for periods from 1 minute up to several hours' soaking.
• a preferred EDDS chelator that can be used herein (also known as ethylenediamine-N,N'-disuccinate) is the material described in U.S. Patent 4,704,233, cited hereinabove, and has the formula (shown in free acid form):
• chelators can be used herein. Indeed, simple polycarboxylates such as citrate, oxydisuccinate, and the like, can also be used, although such chelators are not as effective as the amino carboxylates and phosphonates, on a weight basis. Accordingly, usage levels may be adjusted to take into account differing degrees of chelating effectiveness.
• the chelators herein will preferably have a stability constant (of the fully ionized chelator) for copper ions of at least about 5, preferably at least about 7. Typically, the chelators will comprise from about 0.5% to about 10%, more preferably from about 0.75% to about 5%, by weight of the compositions herein, in addition to those that are stabilizers.
• Preferred chelators include DETMP, DETPA, NTA, EDDS, TPED, and mixtures thereof.
• composition can optionally comprise from about 0.1% to about 50% of by weight of the composition of a color care agent having the formula:
• X is selected from the group consisting of hydrogen, linear or branched, substituted or unsubstituted alkyl having from 1 to 10 carbons atoms and substituted or unsubstituted aryl having at least 6 carbon atoms; n is an integer from 0 to 6; Ri , R2, R3, and R4 are independently selected from the group consisting of alkyl; aryl; alkaryl; arylalk; hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula - ((CH2)yO) z R7 where R7 is hydrogen or a linear, branched, substituted or unsubstituted alkyl chain having from 1 to 10 carbon atoms and where y is an integer from 2 to 10 and z is an integer from 1 to 30; alkoxy; polyalkoxy having the formula: -(O(CH2)y) z R7; the group -C(O)Rg where Rg is alkyl; alkaryl; arylal
• Preferred agents include those where R ⁇ , R2, R3, and R4 are independently selected from the group consisting of alkyl groups having from 1 to 10 carbon atoms and hydroxyalkyl groups having from 1 to 5 carbon atoms, preferably ethyl, methyl, hydroxyethyl, hydroxypropyl and isohydroxypropyl.
• the color care agent has more than about 1% nitrogen by weight of the compound, and preferably more than 7%.
• a preferred agent is tetrakis-(2-hydroxylpropyl) ethylenediamine (TPED).
• the silicone herein can be either a polydimethyl siloxane (polydimethyl silicone or PDMS), or a derivative thereof, e.g., amino silicones, ethoxylated silicones, etc.
• the PDMS is preferably one with a low molecular weight, e.g., one having a viscosity of from about 2 to about 5000 cSt, preferably from about 5 to about 500 cSt, more preferably from about 25 to about 200 cSt Silicone emulsions can conveniently be used to prepare the compositions of the present invention.
• the silicone is one that is, at least initially, not emulsified. I.e., the silicone should be emulsified in the composition itself.
• the silicone is preferably added to the "water seat", which comprises the water and, optionally, any other ingredients that normally stay in the aqueous phase.
• Low molecular weight PDMS is preferred for use in the fabric softener compositions of this invention.
• the low molecular weight PDMS is easier to formulate without pre-emulsification.
• Silicone derivatives such as amino-functional silicones, quatemized silicones, and silicone derivatives containing Si-OH, Si-H, and/or Si-Cl bonds, can be used. However, these silicone derivatives are normally more substantive to fabrics and can build up on fabrics after repeated treatments to actually cause a reduction in fabric absorbency.
• the fabric softener composition When added to water, the fabric softener composition deposits the biodegradable cationic fabric softening active on the fabric surface to provide fabric softening effects.
• cotton fabric water absorbency can be appreciably reduced at high softener levels and/or after multiple cycles.
• the silicone improves the fabric water absorbency, especially for freshly treated fabrics, when used with this level of fabric softener without adversely affecting the fabric softening performance.
• the mechanism by which this improvement in water absorbency occurs is not understood, since the silicones are inherently hydrophobic. It is very surprising that there is any improvement in water absorbency, rather than additional loss of water absorbency.
• the amount of PDMS needed to provide a noticeable improvement in water absorbency is dependent on the initial rewettability performance, which, in turn, is dependent on the detergent type used in the wash. Effective amounts range from about 2 ppm to about 50 ppm in the rinse water, preferably from about 5 to about 20 ppm.
• the PDMS to softener active ratio is from about 2:100 to about 50:100, preferably from about 3:100 to about 35:100, more preferably from about 4:100 to about 25:100. As stated hereinbefore, this typically requires from about 0.2% to about 20%, preferably from about 0.5% to about 10%, more preferably from about 1% to about 5% silicone.
• the PDMS also improves the ease of ironing in addition to improving the rewettability characteristics of the fabrics.
• the fabric care composition contains an optional soil release polymer
• the amount of PDMS deposited on cotton fabrics increases and PDMS improves soil release benefits on polyester fabrics.
• the PDMS improves the rinsing characteristics of the fabric care compositions by reducing the tendency of the compositions to foam during the rinse. Su ⁇ risingly, there is little, if any, reduction in the softening characteristics of the fabric care compositions as a result of the presence of the relatively large amounts of PDMS.
• the present invention can include other optional components conventionally used in textile treatment compositions, for example: colorants; preservatives; surfactants; anti- shrinkage agents; fabric crisping agents; spotting agents; germicides; fungicides; anti- corrosion agents; enzymes such as proteases, cellulases, amylases, lipases, etc; and the like.
• the present invention can also include other compatible ingredients, including those disclosed U.S. Pat. No. 5,686,376, Rusche, et al.; issued November 11, 1997, Shaw, et al.; and U.S. Pat. No. 5,536,421, Hartman, et al., issued July 16, 1996, said patents being inco ⁇ orated herein by reference.
• TEA Di-ester Quat Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the acyl group is derived from partially hydrogenated canola fatty acid l)-Esterification:
• the quatemized material is optionally diluted with e.g. about 68 g of ethanol and about 68 g of hexylene glycol which lowers the melting point of the material thereby providing a better handling of the material.
• Additional ingredients can be added to the material at this time including chelants, antioxidants, perfume, etc. Disclosures of such materials and the benefits of including them can be found in U.S. Pat. 5,747,443, Wahl, Trinh, Gosselink, Letton, and Sivik, issued May 5, 1998 and in U.S. Pat. 5,686,376, Rusche, Baker, and Maashlein, issued Nov. 11, 1997, said patents being inco ⁇ orated herein by reference.
• the above synthesized softener compound is also exemplified below in the non- limiting fabric softening composition examples.
• compositions in the Examples below are made by first preparing an oil seat of softener active at ambient temperature.
• the softener active can be heated, if necessary, to melting, if the softener active is not fluid at room temperature.
• the softener active is mixed using an IKA RW 25 ® mixer for about 2 to about 5 minutes at about 150 rpm.
• a water seat is prepared, i.e., with deionized (DI) water at ambient temperature and with optional acid if needed to adjust pH.
• DI deionized
• the acid/water seat should also be heated to a suitable temperature, e.g., about 100°F (about 38°C) and maintaining said temperature with a water bath.
• the principal solvent(s) melted at suitable temperatures if their melting points are above room temperature
• the softener premix is mixed for about 5 minutes.
• the optional phase stabilizer(s) are added and mixed for about one minute.
• the electrolyte is added and mixed for about one minute.
• the water seat is then added to the softener premix and mixed for about 20 to about 30 minutes or until the composition is clear and homogeneous.
• the perfume is added and mixed until the composition is clear and homogeneous.
• the composition is allowed to air cool to ambient temperature.
• compositions are prepared as follows.
• the components are added in the following order, with thorough mixing after each addition by hand, or with, for example, a Lightnin® 77 mixer for about 2 to about 5 minutes at about 150 ⁇ ra: softener active, principal solvent, optional phase stabilizer, water, perfume, and electrolyte (as concentrated aqueous solution).
• the efficiency of the alkyl ethoxylated surfactants such as Neodols ® correlates well with the HLB (Hydrophilic/Lipophilic Balance) value. The higher the HLB value, the lower the weight percent of Neodol ® that is necessary for the composition.
• HLB Hydrophilic/Lipophilic Balance
• Ethoxylated monoalkyl ammonium ethylsulfate trademarked by Witco
• Alkyl amido propyl amine trademarked by Akzo Nobel
• the above compositions are introduced into containers, specifically bottles, and more specifically clear bottles (although translucent bottles can be used), made from polypropylene (although glass, oriented polyethylene, etc., can be substituted), the bottle having a light blue tint to compensate for any yellow color that is present, or that may develop during storage (although, for short times, and perfectly clear products, clear containers with no tint, or other tints, can be used), and having an ultraviolet light absorber in the bottle to minimize the effects of ultraviolet light on the materials inside, especially the highly unsaturated actives (the absorbers can also be on the surface).
• the overall effect of the clarity and the container being to demonstrate the clarity of the compositions, thus assuring the consumer of the quality of the product.
• the clarity and odor of the fabric softener are critical to acceptance, especially when higher levels of the fabric softener are present.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Materials Engineering (AREA)
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• Crystallography & Structural Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Detergent Compositions (AREA)

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• 1998
  • 1998-11-24 CA CA002310612A patent/CA2310612A1/en not_active Abandoned
  • 1998-11-24 PE PE1998001144A patent/PE132599A1/es not_active Application Discontinuation
  • 1998-11-24 EP EP98962829A patent/EP1036147A1/en not_active Withdrawn
  • 1998-11-24 TR TR2000/01470T patent/TR200001470T2/xx unknown
  • 1998-11-24 JP JP2000522195A patent/JP3866035B2/ja not_active Expired - Fee Related
  • 1998-11-24 BR BR9815323-4A patent/BR9815323A/pt not_active IP Right Cessation
  • 1998-11-24 AU AU17984/99A patent/AU744181B2/en not_active Ceased
  • 1998-11-24 KR KR1020007005674A patent/KR20010032434A/ko not_active Application Discontinuation
  • 1998-11-24 CZ CZ20001814A patent/CZ20001814A3/cs unknown
  • 1998-11-24 ID IDW20001014A patent/ID28312A/id unknown
  • 1998-11-24 CN CN98813263A patent/CN1297474A/zh active Pending
  • 1998-11-24 WO PCT/US1998/025079 patent/WO1999027050A1/en not_active Application Discontinuation
  • 1998-11-25 AR ARP980105957A patent/AR017667A1/es not_active Application Discontinuation
• 2000
  • 2000-09-01 MX MXPA00008622 patent/MXPA00008622A/es unknown
• 2006
  • 2006-03-10 JP JP2006065869A patent/JP4242393B2/ja not_active Expired - Fee Related
  • 2006-03-10 JP JP2006065892A patent/JP4402060B2/ja not_active Expired - Fee Related

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