WO1995032268A1 - Compositions detergentes antimousse - Google Patents

Compositions detergentes antimousse Download PDF

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Publication number
WO1995032268A1
WO1995032268A1 PCT/US1995/004758 US9504758W WO9532268A1 WO 1995032268 A1 WO1995032268 A1 WO 1995032268A1 US 9504758 W US9504758 W US 9504758W WO 9532268 A1 WO9532268 A1 WO 9532268A1
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WIPO (PCT)
Prior art keywords
suds suppressor
suds
detergent composition
carbon atoms
alkyl
Prior art date
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PCT/US1995/004758
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English (en)
Inventor
Richard Timothy Hartshorn
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The Procter & Gamble Company
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Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002189751A priority Critical patent/CA2189751C/fr
Priority to JP7530285A priority patent/JPH10500718A/ja
Priority to US08/737,943 priority patent/US5837670A/en
Priority to AU23880/95A priority patent/AU2388095A/en
Priority to MX9605756A priority patent/MX9605756A/es
Publication of WO1995032268A1 publication Critical patent/WO1995032268A1/fr

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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides

Definitions

  • the present invention relates to detergent compositions having suds suppressing properties. More particularly, the present invention relates to new suds suppressor compounds.
  • Detergent compositions containing high levels of surfactants are known in the art.
  • Surfactants such as anionic, nonionic or cationic are required to aid grease removal and maintain soil suspension from fabrics. More particularly, high levels of anionic surfactants are desirable to provide whiteness maintenance.
  • a problem encountered with the use of some high levels of surfactants, especially high foaming anionic surfactants, is the propensity of the surfactant to give high levels of sudsing; this problem being particularly more acute at high temperature.
  • Peracid precursors are also known for providing more effective bleaching. Particularly effective are the hydrophobic bleach precursor such as Nonanoyl Oxy Benzene Sulphonate (NOBS), which generates a fatty acid by-product in the wash liquor. However, this is ineffective at controlling suds in high temperatures wash conditions.
  • NOBS Nonanoyl Oxy Benzene Sulphonate
  • EP 0170386 teaches amidoperoxy compound and their precursors in a peroxygen bleaching composition which provide effective bleaching of textiles over a wide range of temperatures.
  • amidoperoxy compounds and their precursors such as described in US SN 08/064,563 and EP 0170386 gives further enhanced suds suppressing properties.
  • amidoacid compounds have suds suppressing properties.
  • It is an object of the invention to provide a detergent composition comprising new suds suppressor compounds selected from amidoacid and mixtures of amidoacid and amidoperacid.
  • the present invention encompasses a detergent composition formulated with conventional detersive surfactants, optional builders, detergent adjuncts and a suds suppressor, wherein said suds suppressor is an amidoacid of formula
  • Ri is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.
  • the present invention contemplates detergent compositions having suds suppressing properties.
  • An essential component useful for the purpose of the invention is a suds suppressor compound in a detergent composition formulated with conventional detersive surfactants, optional builders, detergent adjuncts, wherein said suds suppressor is selected from amidoacid and mixtures of amidoacid and amidoperacid.
  • Levels of said surfactants in the detergent composition will typically be from 1 % to 80% by weight of the detergent composition and levels of said suds suppressor from 0.025% to 20% by weight of the detergent composition.
  • the described compounds i.e. amidoacid and mixture of amidoacid and amidoperacid, exhibit excellent suds suppressing properties and may be used as a 'detergent active' suds suppressor or as a co-suds suppressor agent.
  • amidoacid or the mixture of amidoacid and amidoperacid gives also a bleaching activity with or without a bleaching agent.
  • the suds suppressing properties of this development are retained in the presence of organic peroxyacid bleaches derived from mixtures of perhydrates and precursors which contain one or more N-acyl or O-acyl group such as TAED, NOBS, acyl lactam and cationic precursors, or preformed peracids such as amido peracids or diperacids.
  • organic peroxyacid bleaches derived from mixtures of perhydrates and precursors which contain one or more N-acyl or O-acyl group such as TAED, NOBS, acyl lactam and cationic precursors, or preformed peracids such as amido peracids or diperacids.
  • amidoacid and the mixture of amidoacid and amidoperacid show a good suds suppressing activity with surfactants selected from anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • surfactants selected from anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • Especially preferred surfactants are those selected from anionic, nonionic, cationic surfactants and mixtures thereof.
  • surfactants for an enhanced reduction of suds formed from surfactants are nil-LAS surfactants.
  • a main component useful for providing the suds suppressing properties is an amidoacid of formula
  • Ri is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.
  • Another suds suppressor component useful for the present invention is a mixture of amidoacid as described above and amidoperacid of formula
  • W ⁇ is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.
  • Preferred suds suppressors such as described herein before are those wherein RI is an alkyl group containing from 6 to 12 carbon atoms, R2 contains from 1 to 8 carbon atoms, and R5 is H or methyl. Particularly preferred suds suppressors are those of the above general formulas wherein RI is an alkyl group containing from 7 to 10 carbon atoms and R2 contains from 4 to 5 carbon atoms.
  • Level of said suds suppressor in the detergent composition are normally added at a level of from 0.025% to 20%, preferably from 0.05% to 15%, more preferably from 0.06% to 12% and most preferably from 0.06% to 7% by weight of the composition.
  • the detergent compositions in which said suds suppressors can be used include compositions which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin, etc.; for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions.
  • Another aspect of the present invention comprises an aqueous wash liquor containing a detersive surfactant comprising a CiO"C20 a ⁇ yl sulphate, optionally together with builders, detergent adjuncts and a suds suppressor compound wherein said suds suppressor is formed from a suds suppressor precursor of formula
  • Ri is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms
  • L is a leaving group
  • L can be essentially any suitable leaving group.
  • a leaving group is any group that is displayed from the suds suppressor precursor as a consequence of the nucleophilic attack on the suds suppressor precursor by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid suds suppressor.
  • a competing reaction can also occurs which is the hydrolysis reaction. This hydrolysis reaction results in the formation of the carboxylic acid suds suppressor.
  • the nucleophilic attack is provided by the hydroxide anion which provide as for the competing reaction cited above an hydrolysis reaction. This results in the formation of the carboxylic acid suds suppressor.
  • a group to be a suitable leaving group it must exert an electron attracting effect. It should also form a stable entity so that the rate of the back reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion or the hydroxide anion.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this precursor will be difficult to stabilise in detergent composition.
  • Preferred suds suppressor precursors are those of the above general formula wherein RI , R2 and R5 are as defined for the suds suppressor (amidoacid and amidoperacid) and L is selected from
  • RI is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms
  • R3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R4 is H or R3
  • Y is H or a solubilising group.
  • the preferred solubilising groups are -S ⁇ 3"M + , -C ⁇ 2"M + , -S ⁇ 4"M + , -N+(R3)4X- and 0 ⁇ --N(R3)3 and most preferably -S ⁇ 3"M+ and -C02" M + wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the suds suppressor precursor and X is an anion which provides solubility to the suds suppressor precursor.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulphate or acetate anion.
  • X is a halide, hydroxide, methylsulphate or acetate anion.
  • R3 is as defined above and Y is -SO3-M + or -C ⁇ 2"M + wherein
  • L has the general formula:
  • the suds suppressor precursors defined herein before will comprise at least 0.1 %, preferably from 0.1 % to 50%, more preferably from 0.2% to 30% , most preferably from 0.5% to 25% , by weight of the detergent composition.
  • Another embodiment of the present invention is the addition to the detergent composition of the invention of other suds suppressor agents and/ or detersive surfactants.
  • the ratio of said anionic surfactant to said silicone is preferably from at least 10 to 1, more preferably from at least 15 to 1.
  • the anionic surfactant is alkyl sulphate
  • the preferred ratio of said alkyl sulphate to said silicone is from at least 20 to 1.
  • suds suppressors A wide variety of materials, well known to those skilled in the art, may be used as additional or co-suds suppressors. See, for example, Kirk Othmer Encyclopaedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra- alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilise waxy hydrocarbons, preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1,500 cs. at 25°C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO]J2 units and to Si ⁇ 2 units of from 0.6:1 to 1.2:1;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b)
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene gly col/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight % , preferably more than 5 weight % .
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol: copolymer of polyethylene- polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the j-Ci ⁇ alkyl alcohols having a Ci-Ci chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
  • WO 93/17772 Another highly preferred foam regulator system is described in WO 93/17772, which system is a granular free flowing foam regulator containing carrier free from surfactant.
  • the surfactant component is preferably a C12-C22 alkyl sulphate, an alkyl polyglycoside especially based on glucose with a C12-C18 alkyl group and/or an alkali salt of a sulphonation product of a (m)ethyl ester of a C12-C22 fatty acid.
  • the system is free from Si ⁇ 2, the carrier is free from phosphate and is water- soluble or -dispersible, and the paraffin wax is solid at room temperature and up to 100% by weight liquid at below 90°C.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • An exemplary foam regulator system for use herein is granular, free- flowing foam regulator which contains: 1-a granular, surfactant-free carrier, and
  • 2-an adsorbed uniform defoamer mixture free from siloxane polymers and emulsifying or dispersant tensides containing a)-70-95 % by weight of a paraffin wax or mixture and b)-30-5% of a bisamide from C2-C7 diamines and C12-C22 saturated carboxylic acids.
  • antifoam controller is described in WO 94/00547, which antifoam controller is lecithin, preferably soya-lecithin.
  • compositions herein will generally comprise from 0% to 5% of additional suds suppressors.
  • additional suds suppressors When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5% , by weight, of the detergent composition.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimised and effectiveness of lower amounts for effectively controlling sudsing.
  • Preferably from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 5.0% , although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • Nonlimiting examples of surfactants useful herein typically at levels from 1% to 55%, by weight include the conventional Cn-Ci8 alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C ⁇ o-C20 alkyl sulphates (“AS”), the C ⁇ o ⁇ Ci8 secondary (2,3) alkyl sulphates of the formula CH3(CH2) x (CHOS ⁇ 3 ⁇ M + ) CH3 and CH3 (CH2) y (CHOS ⁇ 3 ⁇ M ) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the C10-C18 alkyl alkoxy sulphates (“AE X S”; especially EO 1-7 ethoxy sulphates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 e
  • the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines”), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • AE C12-C18 alkyl ethoxylates
  • sulfobetaines especially ethoxylates and mixed ethoxy/propoxy
  • C10-C18 amine oxides especially C10-C18 amine oxides, and the like
  • Amine oxide is a useful detersive surfactant for the purpose of the invention as it gives a strong cleaning benefit in combination with other detersive surfactants such as Oleyl sarcosinate.
  • Especially preferred, when used in combination with other surfactants, is the C 14 amine oxide.
  • the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 92/06154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. Mixtures of anionic and nonionic surfactants are especially useful.
  • Cationic surfactants can also be used in the detergent compositions herein.
  • Preferred cationic surfactants suitable for the purpose of the invention are Coco N-hydroxyethyl-N,N-dimethyl ammonium salts and choline ester. Other conventional useful surfactants are listed in standard texts.
  • the detergent compositions of the invention may also contain additional detergent components.
  • additional detergent components and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • compositions of the invention may for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions.
  • compositions suitable for use in a machine washing method eg: machine laundry and machine dishwashing methods
  • the compositions of the invention preferably contain one or more additional detergent components selected from bleach activators and preformed peracids, bleaching agents and mixtures thereof.
  • preformed peracids they may be selected from amidoperacid, diperacid and mixtures thereof.
  • the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the detergent composition.
  • These activators contains one or more N- or O-acyl groups and can be selected from a wide range of classes.
  • activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • the nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used.
  • Also included as bleach activators are the benzoyl oxybenzene sulfonate as disclosed in, for example, EP-A-0341947 and cationic derivatives of the benzoyl oxybenzene sulphonates. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • a useful class of bleach activators is the amido suds suppressor precursors of the invention, which may also function as an activator. These activators can additionally be used with other activators such as described herein (NOBS, TAED, benzoxazin activators, acyl lactam activators and cationic activators and mixtures thereof)
  • Another class of 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 preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
  • R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl 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 sodium perbor
  • Another class of preferred bleach activators include the cationic bleach activators, derived from the valerolactam and acyl caprolactam compounds, of formula:
  • the detergent compositions herein may optionally contain bleaching agents.
  • bleaching agents will typically be at levels of from 1 % to 30% , more typically from 5 % to 20% , of the detergent composition, especially for fabric laundering.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Alkali metal perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulphate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.
  • bleaching agent that can be used without restriction encompasses 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, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, 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 and nonyl amido peroxy adipic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalysed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in 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 MnIV2( u "0)3(l ,4,7-trimethyl-l ,4,7-triazacyclononane)2(PF6)2> Mn ⁇ i2( u ⁇ 0)l( u "OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2- (Cl ⁇ 4)2, MnIV 4 ( u -0)6(l ,4,7-triazacyclononane)4(Cl ⁇ 4)4, Mn Mn 1 ⁇ .
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.
  • Adjunct Ingredients can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). The following are illustrative examples of such adjunct materials.
  • Builders - 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.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder. Liquid formulations typically comprise from 5% to 50% , more typically 5% to 30% , by weight, of detergent builder. Granular formulations typically comprise from 10% to 80% , more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si2 ⁇ 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + l-yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2S-2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate” refers to compounds having a plurality of carboxy late groups, preferably at least 3 carboxy lates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt.
  • alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., C12- 18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1-hydroxy- 1,1- diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • Such chelating agents can be selected from the group amino carboxy lates, amino phosphonates, poly functionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethy lenediaminetetracetates , N-hydroxyethy lethy lenediaminetriacetates , nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra- aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21 , 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l ,2-dihydroxy-3,5- disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from 0.1 % to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5% , preferably 0.01 %-l % by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1 ,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio- Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPID ASE, International Bio-Synthetics, Inc. and TERM AM YL, Novo Industries. FUNGAMYL (Novo) is especially useful.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
  • 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. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. , Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P. " Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp. , U.S.A. and Disoynth Co. , The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulphate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • Patent 3,600,319 issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. Patent 3,519,570.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01 % to 5% .
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Dispersing Agents can advantageously be utilized at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerising or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerised acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacry lates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1 :1 , more preferably from 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acry lie/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1 ,000 to 50,000, more preferably from 1,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerisation of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerisation of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably com ⁇ prising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerisation of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end- caps of polymeric soil release agents such as M ⁇ 3S(CH2)nOCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxy ether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release • agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451 , issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the detergent compositions herein, typically from 0.1 % to 5%, preferably from 0.2% to 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy- 1 ,2-pro ⁇ yleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulphonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabiliser, preferably selected from the group xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabiliser preferably selected from the group xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include poly vinyl pyrrolidone polymers, poly amine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are poly vinyls, poly alky lenes, polyesters, poly ethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1:1,000,000.
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerisation. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1 ,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.
  • compositions also may employ a polyvinyl- pyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 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 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxy ethyl
  • R2 is selected from N-2-bis-hydroxy ethyl, N-2- hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • the brightener is 4,4',- bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'- stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA- GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • Rj is anilino
  • R2 is N-2-hydroxyethyl- N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2' -stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6- mo ⁇ hilino-s-triazine-2-yl)amino]2,2' -stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor.
  • Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • other, conventional optical . brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
  • Brightener Any optical brighteners or other brightening or whitening agents known in the art can be inco ⁇ orated at levels typically from 0.05% to 1.2% , by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4- styryl-phenyl)-2H-naptho[l ,2-d]triazoles; 4,4'-bis(l ,2,3-triazol-2-yl)- stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(-benzimidazol-2-yl)ethylene; 1 ,3-diphenyl- ⁇ yrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[l ,2-d]oxazole; and 2- (stilben-4-yl)-2H-naphtho[l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example., in U.S. Patent 4,375,416, Crisp et al, March 1 , 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13-15 ethoxylated alcohol (EO 7) nonionic surfactant.
  • EO 7 ethoxylated alcohol
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactants, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-pro ⁇ anediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
  • the compositions may contain from 5% to 90% , typically 10% to 50% of such carriers.
  • 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 6.5 and 11, preferably between 7.5 and 10.5.
  • Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0.
  • Laundry products are typically at pH 9-11. 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 detergent composition of the present invention is effective in soft and hard water and can be used in a well built formulation, wherein the builder content is at least 125% by weight of the formulation, as well as in a low built formulation, wherein the builder content is less than 15% by weight of the formulation.
  • Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2Na2C ⁇ 3.3H2 ⁇ 2 coated with a mixed salt of formula Na2S ⁇ 4.n.Na2C ⁇ 3 where n is 0.29 and where the weight ratio of percarbonate to mixed salt is 39:1
  • Protease Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S (approx 2% enzyme activity).
  • Lipase Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S (approx 2% enzyme activity)
  • the % suds is measured and calculated using the following expression:
  • % suds height of suds visible through port hole * 100% height of port hole
  • compositions were prepared and tested for sudsing.
  • Composition A formed wash liquor in accordance with the prior art while composition 1 formed wash liquor in accordance with the invention and composition 2 embodiment of the invention show the suds suppression effect of differing types of amidoacid and amidoperacid.
  • compositions are evaluated for sudsing with the suds method described herein before in medium hard water (12° Clark).
  • amidoacid alone gives a a very effective suds suppressing action at the foaming from the surfactant system.
  • compositions A, B, C formed wash liquors in accordance with the prior art while composition 1, 2, 3, 4 formed wash liquors in accordance with the invention show the suds suppression effect of differing levels of amidoacid and amidoperacid.
  • the blend is perhydrolized in its peracid form, said peracid giving the acid.
  • the mixture, of amidoacid and amidoperacid suds suppressor, obtained reduces the foaming of LAS and AS. A better reduction is seen with the foaming of the AS surfactant.
  • compositions A and B formed wash liquors in accordance with the prior art while compositions 1, 2, 3 formed wash liquors in accordance with the invention show the suds suppression effect of differing levels of amidoacid and amidoperacid.
  • Phthalocyanin ppm e sulphonate
  • compositions are evaluated for sudsing with the suds method described herein before and for performance on a range of hydrophobic and body soils by using a launderometer at 40°C with hard water (12°
  • amidoacid and amidoperacid gives a very effective suds suppressing action at the foaming from the surfactant system and also provides effective cleaning performance on hydrophobic soils like lipstick and polish.
  • the detergent composition of the invention is formulated with additional precursor like TAED or benzoyl caprolactam, the suds suppression properties and performance on hydrophobic stains as well as the performance on hydrophilic stains like tea and coffee are retained.
  • compositions A and B formed wash liquors in accordance with the prior art while composition 1, 2, 3 formed wash liquors in accordance with the invention show the suds suppression effect of differing levels of amidoacid and amidoperacid.
  • compositions are evaluated for sudsing with the suds method described herein before in medium hard water (12° Clark).
  • the mixture of amidoacid and amidoperacid suds suppressors obtained from the amido acid precursor is very effective at suppressing the suds of a mixed AS/cationic surfactant system.
  • compositions were prepared and tested for sudsing.
  • Composition A formed wash liquor in accordance with the prior art while composition 1 and 2 formed wash liquors in accordance with the invention show the suds suppression effect of differing levels/types of amidoacid and amidoperacid.
  • compositions are evaluated for sudsing with the suds method described herein before in soft water (3° Clark) and in hard water (18°
  • the mixture of amidoacid and amidoacid suds suppressor obtained from the amido acid precursor is an effective suds suppression agent of high foaming surfactants in hard water, as well as in soft water.
  • the mixture of said suds suppressor agent also gives better suds suppression results than the nonyl amido peroxy adipic acid.
  • compositions were prepared and tested for sudsing and cleaning.
  • Composition A formed wash liquor in accordance with the prior art while compositions 1, 2, 3, 4, 5 formed wash liquors in accordance with the invention show the suds suppression effect of differing levels/types of amidoacid and amidoperacid.
  • compositions are evaluated for sudsing with the suds method described herein before in medium hard water (12° Clark). % suds 100 30 44 60 65 35
  • Both the amidoacid or the mixture of amidoacid and amidoperacid obtained from the amidoacid precursor act as a suds suppressor agent and give effective cleaning performance on hydrophobic soils like lipstick and polish.
  • the percarbonate: amido acid precursor ratio may be varied without detracting significantly from its performance or suds suppressing properties.
  • compositions were prepared and tested for sudsing.
  • compositions 1, 2, 3, 4, 5, 6, 7 formed wash liquors in accordance with the invention show the suds suppression effect of amidoacid and amidoperacid.
  • the mixture of amidoacid and amidoperacid obtained from the amidoacid precursor acts as a very effective suds suppressing agent with various mixed surfactant systems and also gives a good bleaching activity on hydrophobic soils.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Composition détergente constituée de tensioactifs détersifs usuels, d'adjuvants facultatifs, de compléments détergents et d'un antimousse lequel est un acide aminé de formule (I) ou l'un de ses sels métalliques alcalins ou alcalino-terreux ou leurs mélanges, formule dans laquelle R1 est un groupe alkyle, aryle ou alkaryle à 1 à 14 atomes de carbone, R2 est un groupe alkylène, arylène ou alcarylène à 1 à 14 atomes de carbone, et R5 est H ou un groupe alkyle, aryle ou alcarylène à 1 à 10 atomes de carbone. L'invention porte également sur une composition détergente comprenant un mélange d'antimousses amidoacides et amidoperacides et sur une liqueur de lavage aqueuse comportant un tensioactif détergent faite d'un sulfate d'alkyle C10 à C20, associé facultativement à des adjuvants, des compléments détergents et à un composé antimousse formé à partir d'un précurseur.
PCT/US1995/004758 1994-05-21 1995-04-18 Compositions detergentes antimousse WO1995032268A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002189751A CA2189751C (fr) 1994-05-21 1995-04-18 Compositions detergentes antimousse
JP7530285A JPH10500718A (ja) 1994-05-21 1995-04-18 抑泡性を有する洗剤組成物
US08/737,943 US5837670A (en) 1995-04-18 1995-04-18 Detergent compositions having suds suppressing properties
AU23880/95A AU2388095A (en) 1994-05-21 1995-04-18 Detergent compositions having suds suppressing properties
MX9605756A MX9605756A (es) 1995-04-18 1995-04-18 Composiciones detergentes que tienen propiedades de supresion de espumas.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9410225.8 1994-05-21
GB9410225A GB9410225D0 (en) 1994-05-21 1994-05-21 Detergent compositions having suds suppressing properties

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WO1995032268A1 true WO1995032268A1 (fr) 1995-11-30

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GB (1) GB9410225D0 (fr)
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WO (1) WO1995032268A1 (fr)

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JP4147068B2 (ja) * 2002-08-09 2008-09-10 花王株式会社 毛髪洗浄剤組成物
JP5519369B2 (ja) * 2010-03-30 2014-06-11 エステー株式会社 靴用洗浄剤組成物
CN104789196B (zh) * 2015-04-03 2017-07-04 中国石油大学(北京) 一种油基钻井液用润湿剂及其制备方法
CN107308883B (zh) * 2017-06-26 2019-03-01 江南大学 一种由松香基氨基酸表面活性剂形成的稳定泡沫
CN114574295A (zh) * 2022-03-13 2022-06-03 深圳乙奇生物科技有限公司 一种浓缩型光解洗衣液及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50150701A (fr) * 1974-05-24 1975-12-03
US4852989A (en) * 1987-05-08 1989-08-01 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US5328630A (en) * 1991-12-04 1994-07-12 Kao Corporation Liquid detergent composition based on N-acylamino acid potassium salt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50150701A (fr) * 1974-05-24 1975-12-03
US4852989A (en) * 1987-05-08 1989-08-01 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain
US5328630A (en) * 1991-12-04 1994-07-12 Kao Corporation Liquid detergent composition based on N-acylamino acid potassium salt

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CA2189751A1 (fr) 1995-11-30
CN1155899A (zh) 1997-07-30
CN1104488C (zh) 2003-04-02
IN191014B (fr) 2003-09-13
CA2189751C (fr) 2000-06-27
AU2388095A (en) 1995-12-18
GB9410225D0 (en) 1994-07-06
JPH10500718A (ja) 1998-01-20

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