WO1999057236A1 - Utilisation de saponines semi-synthetiques pour la diminution du retrait de tissus fins - Google Patents

Utilisation de saponines semi-synthetiques pour la diminution du retrait de tissus fins Download PDF

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Publication number
WO1999057236A1
WO1999057236A1 PCT/US1999/009719 US9909719W WO9957236A1 WO 1999057236 A1 WO1999057236 A1 WO 1999057236A1 US 9909719 W US9909719 W US 9909719W WO 9957236 A1 WO9957236 A1 WO 9957236A1
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composition
compositions
semi
alkyl
surfactant
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Ashoke Kumar Mitra
Mary Vijayarani Barnabas
Todd Michael Wernicke
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust

Definitions

  • the present invention relates to semi-synthetic saponins and to a method for treating fine fabrics, such as wool, silk, rayon, nylon, linen, polyester and the like, with semi-synthetic saponins for providing the fabrics with improved shrinkage reduction, redeposition reduction, felting reduction, fuzz reduction and/or color appearance.
  • Wool like other fine fabrics, when subjected to water-based laundering, such as typical home laundering, undergoes a gradual felting and severe shrinkage. Accordingly, up to now, wool and other fine fabrics needed to be professionally drycleaned. Therefore, when one wishes to wash the laundry made of these fine fabrics, one must entrust a commercial laundry shop for washing the laundry where a particular detergent and solvent are suitably used for the fine fabrics, such as silks and wools.
  • a detergent and solvent is expensive, environmentally unacceptable and laundry charges include the labor cost, so the cost for the laundry becomes high. Further, in the laundry shop, they accumulate several laundries from different persons and wash them at one time. Some regard this practice as unsanitary.
  • 5,306,435 shrinkproofing agent for fine fabrics, the agent comprising a polyurethane, a salt of divalent to tetravalent metal, a surfactant and auxiliary ingredients such as dispersants, crosslinking agents and the like) to Ishikawa et al.
  • the present invention is a method for imparting anti-shrinkage, anti-fuzz, anti-felting, anti-redeposition and/or color appearance properties to fine fabrics such as wool, silk, linen, rayon, nylon, cotton, acrylic, acetate, etc.
  • the method comprises the step of contacting a fine fabric with an effective amount of a semi- synthetic saponin-containing treating composition such that the treating composition treats the fine fabric.
  • a method for treating a fine fabric in need of treatment comprising contacting the fine fabric with an effective amount of a semi-synthetic saponin-containing treating composition such that the treating composition treats the fine fabric is provided.
  • a method for treating a fine fabric in need of treatment with a semi-synthetic saponin-containing treating composition by use of a washing machine is provided. This method is especially useful under normal home laundering conditions wherein a washing machine is used, rather than hand washing procedures.
  • a method for treating a fine fabric in need of treatment with a semi-synthetic saponin-containing treating composition by spray-treatment of the fabric is provided.
  • a method for treating a fine fabric in need of treatment with a semi-synthetic saponin-containing treating composition by soaking the fabric in the treating composition is provided.
  • a method for treating a fine fabric in need of treatment with a semi-synthetic saponin-containing treating composition by hand washing the fabric is provided.
  • a preferred treating composition in accordance with the present invention comprises one or more semi-synthetic saponins and detergent ingredients.
  • the treating composition is in the form of an aqueous or non-aqueous heavy duty liquid detergent composition.
  • the treating composition may be in the form of a liquid for spray application, or a solid, such as a concentrated stick, for rubbing onto the fine fabric.
  • the treating compositions of the present invention comprise an "effective amount" of a semi-synthetic saponin.
  • An "effective amount" of a semi- synthetic saponin is any amount capable of measurably improving the anti- shrinkage, anti-felting, anti-fuzz, anti-redeposition and/or color appearance properties of a fine fabric, i.e., wool garment, when it is washed in a washing machine by a consumer. In general, this amount may vary quite widely.
  • Fabric care composition(s) herein is meant to encompass generally fabric care compositions and fabric conditioners.
  • the treating compositions of the present invention comprise an effective amount of a semi-synthetic saponin.
  • the treating compositions further comprise detergent ingredients. These treating compositions are useful in the methods of the present invention.
  • a preferred embodiment of the present invention is a method for treating a fine fabric in need of treatment during machine-washing of the fine fabric, wherein the method comprises treating in an automatic washing machine the fine fabric in need of treatment by contacting the fine fabric with a solution containing an effective amount of a semi-synthetic saponin.
  • this method comprises the steps of:
  • an "effective amount of time” herein means the amount of time required for the semi-synthetic saponin-containing treating composition to adequately treat a fine fabric such that the fine fabric acquires improved anti- shrinkage, anti-felting, anti-fuzz, anti-redeposition and/or color appearance properties. Such time can vary quite widely, however, a preferred range of time is from about 10 minutes to about 30 minutes.
  • the washing machine used in the method described herein can be any conventional washing machine known in the art.
  • it can be a specially designed washing machine such as the washing machine described in U.S. Patent No. 5,520,025 to Joo et al.
  • Another embodiment of the present invention is a method for treating a fine fabric in need of treatment, wherein the method comprises soaking the fine fabric in need of treatment in an aqueous solution containing an effective amount of a semi- synthetic saponin for an effective amount of time.
  • this method further comprises manually washing the fine fabric in need of treatment for an effective amount of time such that the aqueous solution containing the semi-synthetic saponin further treats the fine fabric.
  • Yet another embodiment of the present invention is a method for treating a fine fabric in need of treatment, wherein the method comprises contacting the fine fabric in need of treatment with an effective amount of a semi-synthetic saponin- containing treating composition for an effective amount of time such that the treating composition treats the fine fabric.
  • Methods for contacting the fine fabric in need of treatment with the semi-synthetic saponin-containing treating composition include, but are not limited to, spraying on, rolling on, spreading on, rubbing on, brushing on, soaking the fine fabric in the treating composition, and any other suitable methods known in the art.
  • the semi-synthetic saponin is present in the treating composition of the present invention in an amount in the range of from about 0.01% to about 50% by weight of the treating composition, more preferably from about 1% to about 10% by weight of the treating composition. Furthermore, it is desirable that the semi-synthetic saponin is present in the wash, soaking and/or spray-treatment solution in amount in the range of from about 2 ppm to about 2500 ppm, more preferably from about 200 ppm to about 500 ppm.
  • the treating composition can include conventional detergent ingredients, such as one or more of the following ingredients selected from the group consisting of surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, soil release/removal agents, suds suppressors, polyacids, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, carriers and brighteners.
  • conventional detergent ingredients such as one or more of the following ingredients selected from the group consisting of surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizing systems, soil release/removal agents, suds suppressors, polyacids, anti-redeposition agents, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, carriers and brighteners.
  • surfactants such as one or more of the following ingredients selected from the group consisting of surfactants, builders, bleaches, bleach activators, bleach catalysts, enzymes,
  • Non-aqueous based heavy duty laundry detergent compositions containing the semi-synthetic saponin preferably comprise from about 55% to about 98.9% by weight of the detergent composition of a structured, surfactant-containing liquid phase formed by combining:
  • surfactant system comprising surfactants selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof.
  • Aqueous based heavy duty laundry detergent compositions containing the semi-synthetic saponin preferably contain a surfactant system comprising surfactants selected from the group consisting of nonionic detersive surfactants, anionic detersive surfactants, zwitterionic detersive surfactants, amine oxide detersive surfactants and mixtures thereof.
  • the surfactant system typically comprises from about 0.01% to about 50%, preferably from about 0.2% to about 30% by weight of the detergent composition
  • the treating compositions of the present invention can be incorporated into a spray dispenser, or concentrated stick form that can create an article of manufacture that can facilitate the cleaning and/or fabric care or conditioning of fabric.
  • the spray treatment is a "pre-treat", which is followed by a wash cycle
  • the spray treatment treating compositions preferably comprise from about 0.01%) to about 50% of semi-synthetic saponin by weight the of total treating composition, more preferably from about 1% to about 10% of semi-synthetic saponin by weight of the total treating composition.
  • the spray treatment compositions are desired to do the cleaning, as in the case of wash, then the spray treatment compositions preferably comprise from about 2 ppm to about 2500 ppm of the semi-synthetic saponin by weight of the total treating composition, more preferably from about 200 ppm to about 500 ppm of the semi-synthetic saponin by weight of the total treating composition. In the latter case, a brief rinse, not a full wash cycle, is desirable after treatment.
  • Such spray treatment compositions are typically packaged in a spray dispenser.
  • treating compositions of the present invention can also be used as detergent additives. Such additives are intended to supplement or boost the performance of conventional detergent compositions.
  • semi-synthetic saponins impart to the fine fabric improved anti-shrinkage, anti-felting, anti-fuzz, anti-redeposition and/or improved color appearance. These benefits provided by the semi-synthetic saponin improve the appearance and wear of the fine fabric.
  • the semi-synthetic treating compositions of the present invention can be in solid, liquid, paste, gel, spray, or foam forms.
  • the liquid forms can also be in a "concentrated” form.
  • the water content of the "concentrated” form is less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
  • Semi-synthetic Saponin - Suitable semi-synthetic saponins for use with the present invention include, but are not limited to, hydrophobic and hydrophilic semi- synthetic saponins.
  • Hydrophobic semi-synthetic saponins include, but are not limited to, sarsapogenin, hecogenin, oleanolic acid, betulin, the aglycones of the mono- and bisdesmosides of all saponidus species.
  • Hydrophilic semi-synthetic saponins include, but are not limited to, all of the above described hydrophobic semi-synthetic saponins with sugars, such as rhamnose, arabinose, glucose or any other pentose or hexose sugar, attached.
  • a preferred semi-synthetic saponin is diosgenin 5'-hydroxymethyl galactoside.
  • Diosgenin 5 '-hydroxy methyl galactoside is produced by the following reactions. First, reacting acetobromogalactose with diosgenin to produce diosgenin 5'-hydroxymethyl galactoside pentacetate. Second, removing the pentacetates with anhydrous ammonia in 80% methanol and 20%) ethanol at 50°C overnight to produce diosgenin 5'-hydroxymethyl galactoside.
  • Such semi-synthetic saponins and compounds include, but are not limited to, beta-escin, quillaja saponins, diosgenin, and glycerritinic acid.
  • Detergent Ingredients - Optional detergent ingredients can be included in the treating compositions of the present invention.
  • the precise nature of these additional ingredients, and levels of incorporation thereof will depend on the physical form of the treating compositions, and the nature of the cleaning operation for which it is to be used.
  • detergent ingredients examples include, but are not limited to, the following.
  • the semi-synthetic saponin-containing treating compositions of the present invention can be incorporated into non-aqueous, liquid, heavy-duty detergent compositions.
  • Typical non-aqueous, liquid detergent compositions comprise from about 49% to 99.95% by weight of the compositions of a structured, surfactant- containing liquid phase formed by combining: i) from about 1% to 80% by weight of said liquid phase of one or more non-aqueous organic diluents; and ii) from about 20% to 99% by weight of said liquid phase of a surfactant system comprising surfactants selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof.
  • the liquid phase generally comprises from about 52% to about 98.9%, more preferably from about 55% to about 70% by weight of the detergent compositions herein. It is desirable that the liquid phase is surfactant-structured and comprises from about 55% to 98%) by weight of the compositions.
  • the liquid phase herein is preferably formed from one or more non-aqueous organic diluents into which is mixed a surfactant structuring agent which is preferably a specific type of anionic surfactant-containing powder.
  • a surfactant-containing liquid phase will frequently have a density of from about 0.6 to 1.4 g/cc, more preferably from about 0.9 to 1.3 g/cc. 8
  • non-aqueous organic diluents used in this invention may be either surface active (i.e., surfactant) liquids or non-aqueous, non-surfactant liquids referred to herein as non-aqueous solvents and mixtures thereof.
  • solvent is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions herein. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvenf'-containing liquid phase, other components will be present as particulate material dispersed within the "solvenf'-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto. i) Non-aqueous Surfactant Liquids
  • non-aqueous surfactant liquids which can be used to form the liquid phase of the compositions herein include the alkoxylated alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkylpolysaccharides, and the like.
  • Such normally liquid surfactants are those having an HLB ranging from 10 to 16.
  • Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic surfactants.
  • Alcohol alkoxylates are materials which correspond to the general formula:
  • Rl(C m H 2m O) n OH wherein R 1 is a Cg - Ci g alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.
  • R* is an alkyl group, which may be primary or secondary, that contains from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms.
  • the alcohols will be alkoxylated fatty alcohols that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 ethylene oxide moieties per molecule.
  • the alkoxylated fatty alcohols useful in the liquid phase will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase of the compositions herein are commercially marketed under the trade names Neodol 25-7, Neodol 23-6.5 , Neodol 45-11, Neodol 1-5, Neodol 23-9, Neodol 91- 10, Dobanol 91-5 and Dobanol 25-7 by Shell Chemical Company.
  • alcohol alkoxylate nonionic surfactant is utilized as part of the non- aqueous liquid phase in the detergent compositions herein, it will preferably be present to the extent of from about 1% to 60%, more preferably from about 5% to about 40%), most preferably from about 5% to about 35%, of the composition structured liquid phase.
  • the alcohol alkoxylate component will comprise about 5% to 40% of the structured liquid phase.
  • non-aqueous surfactant liquid which may be utilized in this invention are the ethylene oxide (EO) - propylene oxide (PO) block polymers.
  • EO ethylene oxide
  • PO propylene oxide
  • Materials of this type are well known nonionic surfactants which have been marketed under the trade name Pluronic. Examples of other suitable EO-PO block polymer nonionics are described in greater detail in Davidsohn and Milwidsky; Semi-synthetic Detergents, 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S. Patents 2,674,619 and 2,677,700.
  • R— C— N— Z wherein R is a C9.17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof.
  • Such materials include the C 12-C 1 g N-methyl glucamides. Examples are N-methyl N- 1 -deoxyglucityl cocoamide and N-methyl N-l -deoxyglucityl oleamide.
  • Processes for making polyhydroxy fatty acid, amides are know and can be found, for example, in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the disclosures of which are incorporated herein by reference. The materials themselves and their preparation are also described in greater detail in Honsa, U.S. Patent 5,174,937, Issued December 26, 1992.
  • the amount of total liquid surfactant in the preferred surfactant-structured, non-aqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties.
  • the liquid surfactant can comprise from about 35% to 10%, more preferably from about 50% to about 65% of the non-aqueous liquid phase of the compositions herein. 10 ii) Non-surfactant Non-aqueous Organic Solvents
  • the liquid phase of the detergent compositions herein may also comprise one or more non-surfactant, non-aqueous organic solvents.
  • solvents are preferably those of low polarity.
  • low-polarity liquids are those which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate.
  • Suitable types of low- polarity solvents useful in the non- aqueous liquid detergent compositions herein include, but are not limited to, non- vicinal C4-C alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
  • a preferred type of low-polarity solvent for use in the compositions herein comprises the non-vicinal C4-Cg branched or straight chain alkylene glycols, such as hexylene glycol (4-methyl-2,4-pentanediol), 1 ,6-hexanediol, 1,3-butylene glycol and
  • Another preferred type of low-polarity solvent for use herein includes the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-Cg alkyl ethers, such as diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether which are commercially marketed under the trade names Dowanol, Carbitol, and Cellosolve.
  • Another preferred type of low-polarity organic solvent useful herein comprises the lower molecular weight, preferably at least about 150, more preferably from about 200 to about 600 polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • methyl esters having the general formula: Rl-C(O)-OCH3 wherein Ri ranges from 1 to about 18.
  • suitable methyl esters include, but are not limited to, methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.
  • the low-polarity organic solvent(s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein.
  • a solvent component is preferably utilized in an amount of from about 1% to 70%, more preferably from about 10% to about 60%, most preferably from about 20% to about 50% by weight of the liquid phase.
  • the ratio of surfactant to non-surfactant liquids e.g., the ratio of alcohol alkoxylate to low polarity solvent, within a structured, surfactant-containing liquid phase can be used to vary the rheological properties of the detergent compositions eventually formed.
  • the weight ratio of surfactant liquid to non-surfactant organic solvent will range about 50:1 to 1 :50. More preferably, this ratio will range from about 3:1 to 1 :3, most preferably from about 2:1 to 1 :2.
  • the non-aqueous liquid phase of the detergent compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents hereinbefore described a surfactant which is generally, but not necessarily, selected to add structure to the non-aqueous liquid phase of the detergent compositions herein.
  • Structuring surfactants can be of the anionic, nonionic, cationic, and/or amphoteric types.
  • Preferred structuring surfactants are the anionic surfactants such as the alkyl sulfates, the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates.
  • Carboxylate-type anionics include the CI Q-CI g alkyl alkoxy carboxylates
  • Structuring anionic surfactants will generally comprise from about 1% to 30% by weight of the compositions herein.
  • a preferred type of structuring anionic surfactant comprises conventional primary or secondary alkyl sulfate anionic surfactants.
  • Such surfactants are those produced by the sulfation of higher C -C20 fatty alcohols. Examples of alkyl sulfate-containing non-aqueous, liquid detergent compositions are described in Kong-Chan et al.; WO 96/10073; Published April 4, 1996.
  • Alkyl polyalkoxylate sulfates are also known as alkoxylated alkyl sulfates or alkyl ether sulfates. Such materials are those which correspond to the formula:
  • R2-0-(C m H 2m O)n-S0 3 M wherein R ⁇ is a Ci 0-C22 alkyl group, m is from 2 to 4, n is from about 1 to 15, and M is a salt-forming cation.
  • R ⁇ is a C12-C1 g alkyl, m is 2, n is from 12 about 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium.
  • R ⁇ is a Ci 2-C1 g, m is 2, n is from about 1 to
  • alkylammonium and alkanolammonium counterions are preferably avoided when used in the compositions herein because of incompatibility with peroxygen bleaching agents.
  • alkyl polyalkoxylate sulfates-containing non-aqueous liquid detergent compositions are described in Highland et al; PCT Application No. PCT/US96/04223.
  • anionic surfactant for use as a structurant in the compositions herein comprises the linear alkyl benzene sulfonate (LAS) surfactants.
  • LAS surfactants can be formulated into a specific type of anionic surfactant-containing powder which is especially useful for incorporation into the non-aqueous liquid detergent compositions of the present invention.
  • Such a powder comprises two distinct phases. One of these phases is insoluble in the non-aqueous organic liquid diluents used in the compositions herein; the other phase is soluble in the non-aqueous organic liquids.
  • this preferred anionic surfactant-containing powder which can be dispersed in the non-aqueous liquid phase of the preferred compositions herein and which forms a network of aggregated small particles that allows the final product to stably suspend other solid particulate materials, if any, in the composition.
  • Such a preferred anionic surfactant-containing powder is formed by co- drying an aqueous slurry which essentially contains a) one of more alkali metal salts of C ⁇ 0-16 linear alkyl benzene sulfonic acids; and b) one or more non-surfactant diluent salts.
  • a slurry is dried to a solid material, generally in powder form, which comprises both the soluble and insoluble phases.
  • the linear alkyl benzene sulfonate (LAS) materials used to form the preferred anionic surfactant-containing powder are well known materials. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383, incorporated herein by reference. Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium Cl 1 ⁇ 14, e.g., Ci 2 > LAS is especially preferred.
  • the alkyl benzene surfactant anionic surfactants are generally used in the powder-forming slurry in an amount from about 20 to 70%) by weight of the slurry, more preferably from about 20% to 60% by weight of the slurry.
  • the powder-forming slurry also contains a non-surfactant, organic or inorganic salt component that is co-dried with the LAS to form the two-phase anionic surfactant-containing powder.
  • a non-surfactant, organic or inorganic salt component that is co-dried with the LAS to form the two-phase anionic surfactant-containing powder.
  • Such salts can be any of the known sodium, 13 potassium or magnesium halides, sulfates, citrates, carbonates, sulfates, borates, succinates, sulfo-succinates and the like.
  • Sodium sulfate which is generally a bi- product of LAS production, is the preferred non-surfactant diluent salt for use herein. Salts which function as hydrotropes such as sodium sulfo-succinate may also usefully be included.
  • the non-surfactant salts are generally used in the aqueous slurry, along with the LAS, in amounts ranging from about 1 to 50% by weight of the slurry, more preferably from about 5% to 40% by weight of the slurry. Salts that act as hydrotropes can preferably comprise up to about 3% by weight of the slurry.
  • the aqueous slurry containing the LAS and diluent salt components hereinbefore described can be dried to form the anionic surfactant-containing powder preferably added to the non-aqueous diluents in order to prepare a structured liquid phase within the compositions herein.
  • Any conventional drying technique e.g., spray drying, drum drying, etc., or combination of drying techniques, may be employed. Drying should take place until the residual water content of the solid material which forms is within the range of from about 0.5% to 4% by weight, more preferably from about 1%> to 3% by weight.
  • the anionic surfactant-containing powder produced by the drying operation constitutes two distinct phases, one of which is soluble in the inorganic liquid diluents used herein and one of which is insoluble in the diluents.
  • the insoluble phase in the anionic surfactant-containing powder generally comprises from about 10% to 45% by weight of the powder, more preferably from about 15% to 35%) by weight of a powder.
  • the anionic surfactant-containing powder that results after drying can comprise from about 45% to 94%, more preferably from about 60% to 94%, by weight of the powder of alkyl benzene sulfonic acid salts. Such concentrations are generally sufficient to provide from about 0.5% to 60%, more preferably from about 15% to 60%), by weight of the total detergent composition that is eventually prepared, of the alkyl benzene sulfonic acid salts.
  • the anionic surfactant-containing powder itself can comprise from about 0.45% to 45% by weight of the total composition that is eventually prepared.
  • the anionic surfactant- containing powder will also generally contain from about 2% to 50%, more preferably from about 2% to 25% by weight of the powder of the non-surfactant salts.
  • the combined LAS/salt material can be converted to flakes or powder form by any known suitable milling or comminution process.
  • the 14 particle size of this powder will range from 0.1 to 2000 microns, more preferably from about 0.1 to 1000 microns.
  • a structured, surfactant-containing liquid phase of the preferred detergent compositions herein can be prepared by combining the non-aqueous organic diluents hereinbefore described with the anionic surfactant-containing powder as hereinbefore described. Such combination results in the formation of a structured surfactant-containing liquid phase. Conditions for making this combination of preferred structured liquid phase components are described more fully hereinafter in the "Composition Preparation and Use" section. As previously noted, the formation of a structured, surfactant-containing liquid phase permits the stable suspension of colored speckles and additional functional particulate solid materials within the preferred detergent compositions of this invention.
  • nonionic surfactants specifically, polyhydroxy fatty acid amides of the formula:
  • R — C — N — Z wherein R is a 09.17 alkyl or alkenyl, Ri is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative thereof. Examples are N- methyl N-l -deoxyglucityl cocoamide and N-methyl N-l -deoxyglucityl oleamide.
  • Preferred surfactants for use in the detergent compositions described herein are amine based surfactants of the general formula:
  • R4 wherein Ri is a C ⁇ -C] ⁇ alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-0(R5)) wherein 15 R5 is H or methyl.
  • Especially preferred amines based surfactants include the following:
  • R ⁇ is a Cg-Ci ⁇ alkyl group and R5 is H or CH3.
  • Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C -Cj2 bis(hydroxyethyl)amine, Cg-Ci 2 bis(hydroxyisopropyl)amine, Cg-Cj2 amido- propyl dimethyl amine, or mixtures thereof.
  • the amine based surfactant is described by the formula:
  • the present invention also comprises aqueous based liquid detergent compositions.
  • the aqueous liquid detergent compositions preferably comprise from about 10% to about 98%), preferably from about 30% to about 95%, by weight of an aqueous liquid carrier which is preferably water.
  • the aqueous liquid detergent compositions of the present invention comprise a surfactant system which preferably contains one or more detersive co-surfactants in addition to the branched surfactants disclosed above.
  • the additional co-surfactants can be selected from nonionic detersive surfactant, anionic detersive surfactant, zwitterionic detersive surfactant, amine oxide detersive surfactant, and mixtures thereof.
  • the surfactant system typically comprises from about 5% to about 70%, preferably from about 15% to about 30%), by weight of the detergent composition.
  • Anionic surfactants include C ⁇ 1 -Ci g alkyl benzene sulfonates (LAS) and primary, branched-chain and random C10-C20 lkyl sulfates (AS), the CJ O-CI g secondary (2,3) alkyl sulfates of the formula CH3(CH2) x (CHOS0 3 " M + ) CH3 and 16
  • anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent No. 3,919,678, Laughlin et al, issued December 30, 1975.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • examples of this group of semi-synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg-Cj carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
  • anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water- soluble salts of 2-acyloxy-alkane-l -sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula
  • RO(C 2 H 4 0) x S03-M+ wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, 17 especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15.
  • Preferred alkyl sulfate surfactants are the non-ethoxylated Ci 2-15 prim ry and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
  • fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
  • Nonionic and amphoteric surfactants include C12-C1 g alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and Cg-
  • the CjQ-Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C1 g N-methylglucamides. See WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-Ci g N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl Cj2- C1 g glucamides can be used for low sudsing.
  • C10-C2O conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Ci6 soaps may be used.
  • nonionic surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
  • these surfactants include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful.
  • compositions herein also contain amine oxide surfactants of the formula: Rl(EO) x (PO) y (BO) z N(0)(CH 2 R')2-qH2 ⁇ (I)
  • the structure (I) provides one long-chain moiety Rl(EO) x (PO)y(BO) z and two short chain moieties, CH2R'.
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R* is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, Ri is a primary alkyl moiety.
  • Ri is a primary alkyl moiety.
  • R* is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • Ri When x+y+z is different from 0, Ri may be somewhat longer, having a chainlength in the range C 12 ⁇ 24-
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, Ri is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional semi-synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethyl-amine oxide, tetradecyldimethylamine oxide dihydrate, and mixtures thereof.
  • R' is H
  • R is CH2OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
  • the most preferred type of particulate material useful in the detergent compositions herein comprises particles of a peroxygen bleaching agent.
  • a peroxygen bleaching agent may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
  • Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al, Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al., Issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6- oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.
  • NAPAA 6-nonylamino-6- oxoperoxycaproic acid
  • Inorganic peroxygen bleaching agents may also be used in particulate form in the detergent compositions herein.
  • Inorganic bleaching agents are in fact preferred.
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials, most preferably the percarbonates.
  • sodium perborate e.g. mono- or tetra-hydrate
  • Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants.
  • coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
  • Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc.
  • bleach activators which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
  • activators are disclosed in U.S. Patent 4,915,854, 20
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • R 1 N(R 5 )C(0)R 2 C(0)L or R 1 C(0)N(R5)R2C(0)L wherein Ri is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R$ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group, for example, oxybenzene sulfonate, -OOH, -OOM.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenol sulfonate.
  • bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551. Such mixtures are characterized herein as (6-Cg-C ⁇ Q alkamido- caproy l)oxybenzenesulfonate .
  • Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of useful bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • lactam activators include benzoyl 21 caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
  • peroxygen bleaching agents are used as all or part of the particulate material, they will generally comprise from about 0.1% to 30%> by weight of the composition. More preferably, peroxygen bleaching agent will comprise from about 1% to 20% by weight of the composition. Most preferably, peroxygen bleaching agent will be present to the extent of from about 5% to 20% by weight of the composition. If utilized, bleach activators can comprise from about 0.5% to 20%, more preferably from about 3% to 10%, by weight of the composition. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1 :1 to 10:1, more preferably from about 1.5:1 to 5:1. In addition, it has been found that bleach activators, when agglomerated with certain acids such as citric acid, are more chemically stable.
  • compositions herein can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds and levels of use are well known in the art and include, for example, the managanese-based catalysts disclosed in U.S. Pat. No. 5,576,282, U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn ⁇ 2( u O)3( 1,4,7- trimethyl-l,4,7-triazacyclononane)2(PF6)2 3 M n ⁇ 2( u "0)l( -OAc)2(l,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(Cl ⁇ 4)2, Mn 1 V 4(u-O)6( 1,4,7- triazacyclononane)4(Cl ⁇ 4)4, Mn ⁇ Mn 1 V 4(u-O) 1 (u-O Ac)2-( 1 ,4,7-trimethy 1- 1 ,4,7- triazacyclononane)2(Cl ⁇ 4)3, Mn ⁇ (l ,4,7-trimethyl-l ,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936, 5,595,967, 5,703,030 and M. L. Tobe, 22
  • cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein "OAc” represents an acetate moiety and “Ty” is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH 3 ) 5 OAc](OAc)2;
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.
  • compositions herein also optionally, but preferably, contain up to about 50%, more preferably from about 1% to about 40%, even more preferably from about 5% to about 30%, by weight of a detergent builder material. Lower or higher levels of builder, however, are not meant to be excluded.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. Suitable detergent builders are described in U.S. Patent No. 5,576,282, Miracle et al., issued November 19, 1996. U.S. Patent No. 4,321,165, Smith et al, issued March 23, 1982. Preferred builders for use in liquid detergents herein are described in U.S. 23
  • the detergent compositions herein may also optionally contain one or more types of inorganic detergent builders beyond those listed hereinbefore that also function as alkalinity sources.
  • optional inorganic builders can include, for example, aluminosilicates such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; Issued August 12, 1986, the disclosure of which is incorporated herein by reference.
  • crystalline layered silicates such as those discussed in this '509 U.S. patent, are also suitable for use in the detergent compositions herein.
  • optional inorganic detergent builders can comprise from about 2% to 15% by weight of the compositions herein.
  • the detergent compositions according to the present invention comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant can be selected from nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar nonionic surfactants.
  • the surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of detergent compositions in accord with the invention.
  • the surfactant is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • nonionic, anionic, cationic, ampholytic, zwitterionic and semi-polar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950 and 5,576,282.
  • Nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:
  • R 2 - C(O) - N(R 1 ) - Z wherein Ri is H, or Ri is Ci .4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • Ri is methyl
  • R 2 is a straight Cl l-15 alkyl or Cjg.jg alkyl or alkenyl chain such as coconut alkyl or mixtures 24 thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction.
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10- 24 alkyl or hydroxyalkyl group having a CI Q- C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably Cl2" l8 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation.
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%>, preferably from about 3% to about 20% by weight of such anionic surfactants.
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • the detergent compositions of the present invention typically comprise from 0.2% to about 25%>, preferably from about 1% to about 8% by weight of such cationic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%), preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10%> by weight of such zwitterionic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2%> to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula R1NH2 wherein R ⁇ is a Cg-C ⁇ preferably Cg-C ⁇ o alkyl chain or 25
  • R4X(CH 2 )n, X is -O-, -C(O)NH- or -NH- ?
  • R4 is a C 6 -Ci2 alkyl chain n is between 1 to 5, preferably 3.
  • R ⁇ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
  • Preferred amines according to the formula herein above are n-alkyl amines.
  • Suitable amines for use herein may be selected from 1 -hexylamine, 1-octylamine, 1- decylamine and laurylamine.
  • Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.
  • Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R3N wherein RI and R2 are Ci -Cg alkylchains or
  • R3 is either a Cg-C ⁇ , preferably Cg-Cjo alkyl chain, or R3 is R4X(CH2) n , whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C12, n is between 1 to 5, preferably 2-3.
  • R5 is H or C1-C2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1 R2R3N where RI is a C6-C12 alkyl chain,
  • R2 and R3 are C1-C3 alkyl or
  • Ri C-NH — ( CH 2 )— N— ( R 2 ) n 2 wherein Ri is Cg-Ci 2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4
  • Most preferred amines of the present invention include 1-octylamine, 1- hexylamine, 1 -decylamine, l-dodecylamine,C8-10oxypropylamine, N coco 1- 3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and CIO amidopropyldimethylamine.
  • the most preferred amines for use in the compositions herein are 1- hexylamine, 1-octylamine, 1 -decylamine, 1-dodecylamine. Especially desirable are 26 n-dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • the surfactant and surfactant system of the present invention is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • the detergent compositions herein may also optionally contain one or more types of detergent enzymes.
  • Such enzymes can include proteases, amylases, cellulases and lipases. Such materials are known in the art and are commercially available under such trademarks as . They may be incorporated into the non- aqueous liquid detergent compositions herein in the form of suspensions, "marumes" or "prills".
  • Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL” or the microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP.” Suitable enzymes and levels of use are described in U.S. Pat. No. 5,576,282.
  • Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein.
  • Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition.
  • Prills in the compositions of the present invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time.
  • compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or mixtures thereof.
  • proteases are described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; and WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM® and SAVINASE® all from Novo Nordisk A/S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Gist- Brocades of The Netherlands.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent I AM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • lipases such as Ml LIPASE® and LIPOMAX® (Gist-Brocades) and LIPOLASE® and LIPOLASE ULTRA®(Novo) which have found to be very effective when used in combination with the compositions of the present invention. 28
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO 88/09367 (Genencor).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • amylases can be included for removal of carbohydrate- based stains.
  • WO 94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also W094/18314, Genencor, published August 18, 1994 and WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in detergent compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat.
  • amylases including PURAFACT OX AM® described in WO 94/18314, published August 18, 1994 and WO96/05295, Genencor, published Februaury 22, 1996 and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95.
  • ⁇ -amylases examples include TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A/S Denmark.
  • W095/26397 describes other suitable amylases : ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific activity of TERMAMYL® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2%> of active enzyme by weight of the detergent 29 composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates).
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
  • Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 to Novo. The enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. No. 5,576,282.
  • the detergent compositions herein may also optionally contain a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous detergent compositions herein.
  • a chelating agent which serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous detergent compositions herein.
  • Such chelating agents thus serve to form complexes with metal impurities in the composition which would otherwise tend to deactivate composition components such as the peroxygen bleaching agent.
  • Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are described in U.S. Pat. No. 5,576,282.
  • the detergent compositions herein may also optionally contain one or more of the following: polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, 30 fabric softeners, carriers, hydrotropes, processing aids and/or pigments. Suitable examples of such other detergent ingredients and levels of use are found in U.S. Patent No. 5,576,282.
  • the detergent compositions herein can be made by any suitable process known in the art. Examples of such processes are described in U.S. Pat. No. 5,576,282.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the spray-treatment compositions herein are typically packaged in spray dispensers.
  • the spray dispensers can be any of the manually activated means for producing a spray of liquid droplets as is known in the art, e.g. trigger-type, pump- type, non-aerosol self-pressurized, and aerosol-type spray means. It is preferred that at least about 70%>, more preferably, at least about 80%, most preferably at least about 90%) of the droplets have a particle size of smaller than about 200 microns.
  • the spray dispenser can be an aerosol dispenser.
  • Said aerosol dispenser comprises a container which can be constructed of any of the conventional materials employed in fabricating aerosol containers.
  • the dispenser must be capable of withstanding internal pressure in the range of from about 20 to about 110 p.s.i.g., more preferably from about 20 to about 70 p.s.i.g.
  • the one important requirement concerning the dispenser is that it be provided with a valve member which will permit the treating compositions of the present invention contained in the dispenser to be dispensed in the form of a spray of very fine, or finely divided, particles or droplets.
  • a more complete description of commercially available suitable aerosol spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins, issued Apr.8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17, 1971.
  • the spray dispenser is a self-pressurized non-aerosol container having a convoluted liner and an elastomeric sleeve.
  • a self-pressurized spray dispenser can be found in U.S. Pat. Nos.: 5,111,971, Winer, issued May 12, 1992; and 5,232,126, Winer, issued Aug. 3, 1993.
  • Another type of suitable aerosol spray dispenser is one wherein a barrier separates the wrinkle reducing composition from the propellant (preferably compressed air or nitrogen), as is disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981, 31 incorporated herein by reference.
  • a dispenser is available from EP Spray Systems, East Hanover, N.J.
  • the spray dispenser is a non-aerosol, manually activated, pump-spray dispenser.
  • a more complete disclosure of commercially available suitable dispensing devices appears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued Jan. 23, 1990; 4,735,347, Schultz et al., issued Apr. 5, 1988; and 4,274,560, Carter, issued Jun. 23, 1981.
  • the spray dispenser is a manually activated trigger-spray dispenser.
  • a more complete disclosure of commercially available suitable dispensing devices appears in U.S. Pat. Nos.: 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161,288, McKinney, issued Jul. 7, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr. 19, 1994.
  • a broad array of trigger sprayers or finger pump sprayers are suitable for use with the compositions of this invention. These are readily available from suppliers such as Calmar, Inc., City of Industry, California; CSI (Continental Sprayers, Inc.), St. Peters, Missouri; Berry Plastics Corp., Evansville, Indiana - a distributor of Guala ® sprayers; or Seaquest Dispensing, Cary, 111.
  • the preferred trigger sprayers are the blue inserted Guala ® sprayer, available from Berry Plastics Corp., the Calmar TS800-1 A® sprayers, available from Calmar Inc., or the CSI T7500® available from Continental Sprayers Inc., because of the fine uniform spray characteristics, spray volume and pattern size.
  • Any suitable bottle or container can be used with the trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape to the Cinch® bottle. It can be made of any materials such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass or any other material that forms bottles. Preferably, it is made of high density polyethylene or polyethylene terephthalate.
  • a finger pump can be used with canister or cylindrical bottle.
  • the preferred pump for this application is the cylindrical Euromist II® from Seaquest Dispensing.
  • Product/Instructions - This invention also encompasses the inclusion of instructions on the use of the semi-synthetic saponin-containing treating compositions with the packages containing the treating compositions herein or with other forms of advertising associated with the sale or use of the treating compositions.
  • the instructions may be included in any manner typically used by consumer product manufacturing or supply companies. Examples include providing 32 instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other written or oral instructions which may be connected to the purchase of the treating compositions.
  • the instructions may include information relating to the temperature of the wash water; washing time; recommended settings on the washing machine; recommended amount of the treating composition to use; pre-soaking procedures; and spray-treatment procedures.
  • a product comprising a semi-synthetic saponin-containing treating composition, the product further including instructions for using the treating composition to treat a fine fabric in need of treatment, the instructions including the step of: contacting said fine fabric with an effective amount of said treating composition for an effective amount of time such that said composition treats said fine fabric.
  • the product may be a laundry detergent composition , a fine fabric care composition or fabric conditioner. Furthermore, the product may be contained in a spray dispenser.
  • compositions of the present invention are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.
  • the enzyme levels are expressed by percent of pure enzyme by weight of the total composition and unless otherwise specified, the detergent ingredients are expressed as percent of detergent ingredients by weight of the total compositions.
  • the abbreviated component identifications herein have the following meanings: LAS : Sodium linear C 12 alkyl benzene sulphonate
  • TAS Sodium tallow alkyl sulphate
  • Soap Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut oils. 33
  • Nonionic C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxy lation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh.
  • Neodol 45-13 C14-C15 linear primary alcohol ethoxylate sold by Shell
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m.
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size between 400 ⁇ m and l200 ⁇ m.
  • Citric Anhydrous citric acid PB1 Anhydrous sodium perborate monohydrate bleach, empirical formula NaB ⁇ 2-H2 ⁇ 2
  • TAED Tetraacetyl ethylene diamine.
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.
  • Photoactivated Bleach Sulfonated zinc phtalocyanine encapsulated in dextrin soluble polymer.
  • Protease Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO91/06637 and/or WO95/10591 and or EP 251 446.
  • Amylase Amylolytic enzyme sold under the tradename Purafact Ox Am R described in WO 94/18314, WO96/05295 sold by Genencor;
  • Termamyl®, Fungamyl® and Duramyl® all available from Novo Nordisk A/S and those described in W095/26397.
  • Lipase Lipolytic enzyme sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2-yl) stilbene-2:2'-disulfonate.
  • SRP 1 Sulfobenzoyl or sodium isethionate end capped esters with oxy ethylene oxy and terephtaloyl backbone.
  • liquid detergent formulations according to the present invention are prepared:
  • a series of initial laundrometer tests (1 -cycle at 30°C for 15 minutes (5 minute pre-soak followed by 10 minute wash, 6 gpg) with swatches of challis rayon is performed to observe the shrinkage of the rayon in Woolite®, commercially available from Reckitt and Coleman, compared to the shrinkage of rayon in a semi- 38 synthetic saponin-containing treating composition of the present invention; namely diogenin 5'-hydroxymethyl galactoside; 200 -500 ppm dissolved in dimethyl sulfoxide, 1% TTW, the commercial equivalent for fine fabric care.
  • the results of the tests show that the semi-synthetic saponin-containing treating composition significantly reduced the amount of shrinkage of the rayon as compared to Woolite®.
  • Example 4 A tergetometer test under similar conditions as in Example 4 is performed. In this test, jersey knit wool swatches are used, and the shrinkage of such swatches is observed after treating separate swatches with water, 1% dimethyl sulfoxide, and the semi-synthetic saponin-containing treating composition of Example 4, respectively. The results of the test show that the semi-synthetic saponin-containing treating composition reduced the amount of shrinkage of the wool as compared to both water and 1%) dimethyl sulfoxide compositions.

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Abstract

L'invention concerne des compositions de traitement comprenant des compositions détergentes pour la lessive et des compositions d'entretien des tissus, ainsi que des procédés d'utilisation de ces compositions pour traiter des tissus fins. Ces compositions de traitement contiennent des saponines semi-synthétiques. Ces compositions peuvent être utilisées avec des tissus fins, tels que la laine, la soie, la rayonne, le nylon, le lin, le polyester et analogues, pour en améliorer la diminution du retrait, la diminution du feutrage, la diminution de la formation de duvet et/ou l'apparence des couleurs
PCT/US1999/009719 1998-05-04 1999-05-04 Utilisation de saponines semi-synthetiques pour la diminution du retrait de tissus fins Ceased WO1999057236A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974862A (zh) * 2015-06-15 2015-10-14 马建剑 一种新型羊毛衣物用杀菌防虫洗涤剂及其制备方法
WO2021185870A1 (fr) * 2020-03-19 2021-09-23 Unilever Ip Holdings B.V. Composition détergente
WO2021249927A1 (fr) * 2020-06-08 2021-12-16 Unilever Ip Holdings B.V. Procédé d'amélioration de l'activité protéase

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JPS59179597A (ja) * 1983-03-31 1984-10-12 ライオン株式会社 液体洗浄剤
JPS59182899A (ja) * 1983-04-01 1984-10-17 ライオン株式会社 シヤンプ−組成物
JPS59207994A (ja) * 1983-05-12 1984-11-26 ライオン株式会社 液体洗浄剤
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JPS59179597A (ja) * 1983-03-31 1984-10-12 ライオン株式会社 液体洗浄剤
JPS59182899A (ja) * 1983-04-01 1984-10-17 ライオン株式会社 シヤンプ−組成物
JPS59207994A (ja) * 1983-05-12 1984-11-26 ライオン株式会社 液体洗浄剤
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DATABASE WPI Section Ch Week 8448, Derwent World Patents Index; Class A96, AN 84-296986, XP002900587 *
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974862A (zh) * 2015-06-15 2015-10-14 马建剑 一种新型羊毛衣物用杀菌防虫洗涤剂及其制备方法
WO2021185870A1 (fr) * 2020-03-19 2021-09-23 Unilever Ip Holdings B.V. Composition détergente
CN115298295A (zh) * 2020-03-19 2022-11-04 联合利华知识产权控股有限公司 洗涤剂组合物
WO2021249927A1 (fr) * 2020-06-08 2021-12-16 Unilever Ip Holdings B.V. Procédé d'amélioration de l'activité protéase
CN115698246A (zh) * 2020-06-08 2023-02-03 联合利华知识产权控股有限公司 提高蛋白酶活性的方法
EP4162018B1 (fr) 2020-06-08 2024-01-31 Unilever IP Holdings B.V. Composition de détergent

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