MXPA02005747A - Compositions including ether capped poly(oxyalkylated) alcohol surfactants. - Google Patents

Compositions including ether capped poly(oxyalkylated) alcohol surfactants.

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Publication number
MXPA02005747A
MXPA02005747A MXPA02005747A MXPA02005747A MXPA02005747A MX PA02005747 A MXPA02005747 A MX PA02005747A MX PA02005747 A MXPA02005747 A MX PA02005747A MX PA02005747 A MXPA02005747 A MX PA02005747A MX PA02005747 A MXPA02005747 A MX PA02005747A
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Mexico
Prior art keywords
group
composition
surfactant
substituted
carbon atoms
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MXPA02005747A
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Spanish (es)
Inventor
William Michael Scheper
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Procter & Gamble
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Publication of MXPA02005747A publication Critical patent/MXPA02005747A/en

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0431—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing aromatic rings
    • B01D19/0436—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing aromatic rings with substituted groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0463—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing rings other than aromatic rings
    • B01D19/0468—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance containing rings other than aromatic rings with substituted groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0078—Compositions for cleaning contact lenses, spectacles or lenses
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/06—Paper forming aids
    • D21H21/12—Defoamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

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  • Pharmacology & Pharmacy (AREA)
  • Detergent Compositions (AREA)

Abstract

Compositions including ether capped poly(oxyalkylated) alcohol surfactants having superior grease cleaning abilities and improved spotting filming benefits are provided.

Description

COMPOSITIONS THAT INCLUDE POLYOXY ALCOHOL SURELY AGENTS) BLOCKED WITH ETHER TECHNICAL FIELD The present invention relates to detergent compositions having low foaming nonionic surfactants and very particularly to dishwashing compositions or hard surfaces having ether blocked poly (oxyalkylated) alcohol surfactants having stain removal and of superior film in dishwashing and hard surface cleaning applications.
BACKGROUND OF THE INVENTION Due to the varied nature of different cleaning compositions, different surfactants are better suited for some applications while being less suitable or totally unsuitable for other applications. Nonionic surfactants, such as ethoxylated alcohols, alkyl polyglycosides and alkyl glucosamides are of considerable importance in detergent products. For example, under some conditions, non-ionic surfactants help to cleanse greasy dirt and inhibit the formation of soap and calcium. However, conventional nonionic surfactants designed for effective cleaning in laundry products form liquid crystalline phases when mixed with water. These phases can impede the mixing speed with water and lead to undesirable optical properties of thin films when the solution is dried. For example, conventional non-ionic sprayed on the surface of granules to achieve target density can give rise to a poor granule solution and leave residues in the horizontal axis machine dispensers. Conventional nonionics formulated at high levels in liquid products can lead to poor mixing speeds with water and consumer concern. Conventional nonionics in window and floor cleaners can form visible liquid crystalline films upon drying which increases the effort made by the consumer to achieve good results. Similarly, a nonionic surfactant for use in an automatic dishwashing machine would need to minimize the production of foam and not leave undesirable spots and films on the cleanable surfaces. By considering the above technical constraints as well as the needs and demands of the consumer, the compositions of the product are continuously changing and improving. In addition, environmental factors such as the need for biodegradable materials, the restriction of phosphate, the convenience of providing even better cleaning results with less product, providing less demand for thermal energy and less water ** + - > -To help the washing process, they have all driven the need for improved compositions. Accordingly, there remains a need for some surfactants that are suitable for use in a variety of compositions that can provide improved dissolution of solid products (such as sticks and tablets) and granulated products, improved mixing rates with water as with liquid products, performance of betas and improved film removal as in hard surface cleaners and automatic dishwashers, good cleaning, foam control and good biodegradability while avoiding incompatibility with other cleaning surfactants and / or bleaches.
TECHNICAL BACKGROUND Patent of E.U.A. 4,272,394, WO 94/22800, WO 93/04153, WO96 / 00253 and WO 98/17379.
BRIEF DESCRIPTION OF THE INVENTION This need is met by the present invention, wherein detergent compositions and in particular bleaching, dishwashing or hard surface compositions having low foaming nonionic surfactant are provided. The compositions employ the novel surfactants of the present invention, either alone or in combination with other surfactants, to provide improved film and stain removal performance as well as improved cleaning performance over greasy soils and foams or foam suppression in certain applications. While not wishing to be bound by theory, it is believed that the alcohol surfactants of the present invention provide superior stain and film removal benefits through improved laminating action. As regards the improved cleaning performance on greasy soils, said benefits are shown when the surfactants of the present invention are optionally employed together with a high-point non-ionic surfactant, an amphoteric agent or an anionic surfactant. hydrophobic, as described here in more detail. Lastly, certain alcohol surfactants of the present invention may also act to reduce foaming or foaming associated with food stains or some other cleaning agents. According to a first aspect of the present invention, a detergent composition comprising an ether-blocked poly (oxyalkylated alcohol) surfactant is provided. The composition comprises: (a) from about 0.01% to about 50%, preferably from about 0.1% to about 20%, most preferably from about 0.1% to about 10% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R 1 O) xCH (CH 3) OR 2 wherein R is selected from the group consisting of radicals 5 linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbons having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of alkylene from C2 to C branched or linear in any given molecule; x is a number of 1 to 10 about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms; and 20 (b) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient. According to a second aspect of the present invention, an auxiliary rinsing composition is provided for automatic washing of * - - * faa * 'tar rrT, ® ^ t,. ,. . dish comprising a poly (oxyalkylated alcohol) surfactant blocked with ether. The auxiliary rinsing composition comprising: (a) from about 0.01% to about 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R 1 O) xCH (CH 3) OR 2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C2 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms; Y & amp; _____ i (b) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient; and (c) from about 0.1% to about 99% by weight of the composition of an aqueous liquid vehicle. According to a third aspect of the present invention, there is provided a bleaching composition comprising a poly (oxyalkylated alcohol) surfactant blocked with ether. The bleaching compositions comprise: (a) from about 0.01% to about 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R1O) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; Y . . J.I to aaAMafaa (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms; and (b) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient; and (c) from about 0.1% to about 99% by weight of the composition of a bleaching system. According to a fourth aspect of the present invention, a detergent composition comprising an ether-blocked poly (oxyalkylated alcohol) surfactant is provided. The composition comprises: (a) from about 0.01% to about 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO ( R1O) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C2 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; (b) from about 0.1% to about 99% by weight of the composition of an amine oxide co-surfactant; and (c) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient. According to a fifth aspect of the present invention, a detergent composition comprising an ether-blocked poly (oxyalkylated alcohol) surfactant is provided. The composition comprises: (a) from about 0.01% to about 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO ( R1O) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C2 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; (b) from about 0.1% to about 99% by weight of the hydrophobic co-surfactant composition, wherein said hydrophobic co-surfactant has either an HLB value of less than or equal to 12, preferably less than or equal to 8 or a Kraft temperature greater than about 20 ° C, most preferably greater than about 30 ° C; and (c) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient. According to a sixth aspect of the present invention, a detergent composition comprising an ether-blocked poly (oxyalkylated alcohol) surfactant is provided. The composition comprises: (a) from about 0.01% to about 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: (R1O) xCH (CH3) OR2 wherein R is selected from the group consisting of unsubstituted or substituted, saturated or unsaturated, linear or branched aliphatic or aromatic hydrocarbon radicals, having from about 1 to about 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C2 alkylene in any given molecule; x is a number from 1 to about 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic hydrocarbon radicals having from about 1 to about 30 carbon atoms; (b) from about 0.1% to about 99% by weight of the composition of an adjunct ingredient; wherein said composition comprises less than 1% dialkoxylated acetal of the formula: RO (R 1 O) xCH (CH 3) (OR 1) xOR t? - M? rittftwi1r? n? Aa? ? ^ C ***** where each x is an independently selected number from 1 to about 30; and R and R1 are defined as before. These and other aspects, features and advantages will be apparent to those skilled in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees centigrade (° C) unless otherwise specified. All the cited documents are partly important incorporated herein by reference. 10 DETAILED DESCRIPTION OF THE INVENTION Again, the first aspect of the present invention is directed to a low foaming nonionic surfactant for use in detergent compositions. The surfactant of the present invention has the formula: RO (R 1 O) xCH (CH 3) OR 2 In one aspect of the present invention R is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical, substituted or unsubstituted, having about 1 to about 20 carbon atoms, most preferably still R is a linear or branched, saturated aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms.
"My? < HaMMÉMat? JMa < rt ¿, t. i. ^. . , *? ^.? > . In one aspect of the present invention, R, R1 and R2 are selected such that the poly (oxyalkylated alcohol) surfactant blocked with ether contains one or more chiral carbon atoms. In one aspect of the present invention, the poly (oxyalkylated alcohol) surfactant blocked with ether is a mixture of poly (oxyalkylated) alcohol surfactants blocked with ether. This mixture can be obtained in a variety of ways. For example, by mixing two poly (oxyalkylated alcohol) surfactants with ether, forming the poly (oxyalkylated) alcohol surfactant blocked with ether from a mixture of alcohols, the reaction used to produce the alcohol surfactant poly (oxyalkylated) blocked with ether forms a racemic mixture or by alkoxylation under conditions such that the poly (oxyalkylated) alcohol surfactant blocked with ether produced is a mixture with a range of different alkoxy groups present in each surfactant. This example is intended to be illustrative and in no way limit the scope of the invention. In one aspect of the present invention, R is a hydrocarbon radical of the formula: R4 R5 R6 CH3 (CH2) qCH (CH2) rCH (CH2) $ CH (CH2) tCHz 3 > 6 * «£ *. wherein R4, R5 and R6 are each independently selected from hydrogen, and C1-C3 alkyl, most preferably hydrogen, CrC2 alkyl, most preferably still hydrogen, and mephyl, provided that R4, R5 and R6 are not all hydrogen, when t is 0, at least R4 or R5 is not hydrogen; q, r, s, t are each independently integers from 0 to 13. In a more preferred form of this aspect R is selected from the formulas: CH 3 CH 3 (CH 2) n CH (CH 2) m CH 2 -) CH 3 CH 3 CH 3 (CH 2) jCH (CH2) CHCH2- wherein n, m, y and k are each independently integers from 0 to 13. In one aspect of the present invention R2 is a hydrocarbon radical of the formula: - C (CH3) 2R3 R3 is selected from the group consisting of aliphatic hydrocarbon radicals or linear or branched, saturated or unsaturated, substituted or unsubstituted aromatics having from about 1 to about 30, most preferably 1 to 20, most preferably still from 1 to 15, carbon atoms. In one embodiment of this aspect of the invention, R3 is CH2CH3. In the novel compounds of the present invention, when R2 is (i) then either at least one of R1 is different from the alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms. That is, when R2 is (ii) either a linear or branched aliphatic or aromatic hydrocarbon radical., saturated or unsaturated, substituted or unsubstituted having from about 6 to about 30 carbon atoms or linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms; carbon with at least one of R1 being different from alkylene of C2 to C3. For example, when R2 is a hydrocarbon of the formula: - (CH2) and -X where y and X are described below, or R2 is a hydrocarbon radical of the formula: - C (CH3) 2R3 wherein R3 is described above , then at least one of R1 is different from alkylene of C2 to C3. For example, if x is 5 and R2 is (CH2) and X, then the poly (oxyalkylated) alcohol blocked with ether could have the formula: RO (CH2CH (CH2CH3) 0) 5CH (CH3) O- (CH2) and -X or RO (CH2CH2?) 4 (CH2CH (CH2CH3) O) CH (CH3) O- (CH2) and -X or RO (CH2CHCH3?) (CH2CH (CH2CH3) O) 4CH (CH3) O- (CH2) and - X Similarly, for example if R2 is -C (CH3) 2R3 and x is 7, then the poly (oxyalkylated) alcohol blocked with ether could have the formula: RO (CH2CH2?) 6 (CH2CH2 (CH2CH3) O) CH ( CH3) O- C (CH3) 2R3 or RO (CH2CHCH3?) 4 (CH2CH (CH2CH3) 0) 3CH (CH3) O- C (CH3) 2R3 or RO (CH2CH2?) 3 (CH2CHCH3?) 2 (CH2CH (CH2CH3 ) O) (CH2CH (CH2CH2CH3) O) CH (CH3) O- C (CH3) 2R3 Those above examples are included simply for illustrative purposes and are not intended to be considered in any way as limiting the scope of the present invention. In one aspect of the present invention, R 2 is a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms. In one embodiment of this aspect of the invention, the heteroatoms are selected from the group comprising oxygen, nitrogen, sulfur and mixtures thereof. In one embodiment of this aspect of the invention, R 2 is a 5- to 6-membered heterocycle. In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: wherein each R7 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon or alkoxy radical having from about 1 to about 10 carbon atoms, or R7 is an alicyclic radical or saturated or unsaturated, substituted or unsubstituted aromatic having from about 1 to about 10 carbon atoms, which is fused to the heterocyclic ring; each A is independently selected from the group consisting of O and N (R8) a, wherein R8 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon radical having from about from 1 to about 10 carbon atoms, it is either 0 to 1; z is an integer from 1 to 3. In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: - $ &&&&&> & * é- ~, k * where R7 is defined as before. In another embodiment of this aspect of the present invention R2 is selected from the group consisting of: wherein R7 and R8 are as defined above. In another embodiment of this aspect of the present invention R is selected from the group consisting of: In another embodiment of this aspect of the present invention, R 2 is selected from the group consisting of: In another aspect of the present invention, R 2 is a substituted or unsubstituted polycyclic ring of 7 to 13 members. In one embodiment of this aspect of the present invention, R 2 is selected from the group consisting of unsubstituted or substituted adamantane, substituted or unsubstituted norbornane, substituted or unsubstituted nortricyquin, and substituted or unsubstituted bicyclo [2.2.2] octane. In another embodiment of this aspect of the present invention, R2 is a substituted or unsubstituted adamantane. In one aspect of the present invention, R 2 is a hydrocarbon of the formula: -iCH 2) X-X wherein y is an integer from 0 to 7, X is a substituted or unsubstituted, saturated or unsaturated cyclic or aromatic hydrocarbon radical of 4 to 8 members. In another embodiment of this aspect of the present invention, y is an integer from 1 to 2, and X is selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon radical of 5 to 8 members. In another embodiment of this aspect of the present invention, y is 0 and X is a substituted or unsubstituted, saturated or unsaturated, 5- or 6-membered cyclic or aromatic hydrocarbon radical. In another embodiment of this aspect of the present invention, X is selected from the group consisting of: fc - ta .le wherein each R is independently selected from the group consisting of hydrogen, aliphatic hydrocarbon radical or straight or branched, saturated or unsaturated, substituted or unsubstituted alkoxy radical of from about 1 to about 10 carbon atoms, or R9 is an alicyclic hydrocarbon radical or saturated or unsaturated, substituted or unsubstituted aromatic having from about 1 to about 10 carbon atoms, which is fused to the ring; w is an integer from 1 to 3. In another aspect of this aspect of the present invention, X is selected from the group consisting of: where R is as defined above. In another embodiment of this aspect of the present invention, X is selected from the group consisting of: - & fe.i 1 ^ In one aspect of the present invention, R2 is a linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic or aromatic hydrocarbon radical having from about 1 to about 30 carbon atoms, most preferably R2 is a linear aliphatic hydrocarbon radical or branched, saturated or unsaturated, substituted or unsubstituted having from about 1 to about 20 carbon atoms, most preferably R2 is a linear or branched, saturated aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms. In one aspect of the present invention, when x is greater than 2, R1 may be the same or different. That is, R1 may vary between any of the alkylenoxy units as described above. For example, if x is 3, R1 can be selected to form ethyleneoxy (EO) or propyleneoxy (PO) and can vary from the order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer three is chosen for example alone and the variation can be much greater with a higher integer value for x and includes, for example, multiple units (EO) and a very small number of units (PO). Similarly, ethylene and propylene are chosen, and the variation can be much i .: higher with the selection of linear or branched butylene, pentylene, hexylene and / or heptylene. The surfactants of the present invention can be prepared by a variety of different methods. In one aspect of the present invention, the surfactants can be prepared by reacting a vinyl ether of the formula: R2OCH = CH2 wherein R2 is as defined above; with an alkoxylated alcohol of the formula RO (R 1 O) x H wherein R, R 1, and x, are as defined above, in the presence of a catalyst to form the poly (oxyalkylated) alcohol blocked with ether. In one embodiment of this aspect of the present invention, the step of reacting vinyl ether with alkoxylated alcohol is conducted in the presence of a catalyst. Suitable catalysts include Lewis acids; acids and their salts, both organic and inorganic; pyridinium salts; polymers; clays, such as Spanish sepiolite clay, GIRDLER K-10; aluminosilicates or zeolites, such as zeolite HZS-360, zeolite H-Y; activated carbon such as sulphonated charcoal; transition metal complexes such as molybenzoyl acetylacetone (VI); transition metal salts such as lanthanum trichloride, ceric ammonium nitrate; 2,3-dichloro-5,6, dicyano-p-benzoquinone; bis (trimethylsilyl) sulfate, and mixtures thereof.
Suitable Lewis acids include, but are not limited to, TiCl4, Ti (O'Pr) 4, ZnCl2, SnCl2, AICI3, platinum dichloride, copper chloride (ll), phosphorus pentachloride, phosphorus trichloride, chloride of cobalt (ll), zinc oxide, iron chloride (ll) and BF3-OEÍ2. Suitable inorganic acids include mineral acids such as phosphoric acid, sulfuric acid, hydrochloric acid, phosphorus oxychloride, aluminum phosphate and ammonium chloride. In addition, the mineral acids and their salts may optionally be adsorbed onto a substrate such as silica gel, or alumina. For example, sulfuric acid adsorbed on silica gel or alumina impregnated with zinc chloride. Suitable organic acids include: carboxylic acids such as acetic acid, oxalic acid, glycolic acid, citric acid, tartaric acid, glycolic acid, maleic acid, oxydisuccinic acid; halogenated carboxylic acids such as trifluoroacetic acid, heptafluorobutyric acid, dichloroacetic acid and trichloroacetic acid; and sulfonic and sulfinic acids and their salts such as p-toluenesulfonic acid, toluensulfinic acid, methanesulfonic acid, 4-bromobenzenesulfonic acid, naphthalene sulfonic acid, (±) -IO-camphor sulphonates and alkylbenzenesulfonic acid. The pyridinium salts include, but are not limited to pyridinium p-toluensulfonate (PPTS), pyridinium p-toluensulfinate, pyridinium hydrochloride, pyridinium bromohydrate, pyridinium acid bisulfate, pyridinium acid sulfate and mixtures thereof. raaft í.iáiSg toiAaaM ». .,, i -. 1 i í.: -.,. ^ -; :? ¡, ..,:,:. The suitable transition metal includes, but is not limited to, molybdenyl acetylacetone (VI); transition metal salts such as lanthanum trichloride, ceric ammonium nitrate; 2,3-dichloro-5,6, dicyano-p-benzoquinone, mercury acetate (II), mercury (II) trifluoroacetate, copper acetylacetonate (II) and tetracarbonylbis (cyclopentadienyl) difier. Suitable polymers include but are not limited to polymer ion exchange resins or polyvinyl pyridines. Suitable polymer ion exchange resins include those from the Amberylst series, such as AMBERYLST® 15, available from Rohm & Haas, the DOWEX® series such as, DOWEX 50X8-50 available from Dow; REILLEX 424, available from Reilly Industries; the Amberlite series, such as AMBERLITE IRA-400, or AMBERLITE IR-118, available from Rohm & Hass; available from United Catalyst; the ENVIROCAT series, such as ENVIROCAT EPZG, available from Contract Chemicals; and combinations thereof. Suitable polyvinylpyridines can be substituted or unsubstituted, such as substituted in the vinyl group and / or in the pyridine ring. Examples of suitable vinyl pyridines include, but are not limited to, poly (4-vinylpyridine) triluoromethanesulfonate, poly (2-vinylpyridine) trifluoromethanesulfonate, poly (4-vinylpyrridine) p-toluenesulfonate, poly (p-toluene sulfonate) 2-vinylpyridine), poly (4-vinylpyridine) chloride, poly (2-vinylpyridine) chloride, poly (4-vinylpyridine) bromide, poly (2-vinylpyridine) bromide, and mixtures thereof. These polymeric catalysts have the advantage of being easy to separate from the surfactant produced.
Other suitable catalysts include bis (trimethylsilyl) sulfate, iodotrimethylsilane, allytrimethylsilane, hexamethyldisilane, iodine sulfate, bromine, iron (ll), triphenylphosphine, aluminum sulfate, alkyl sulfuric acids, ether, alkylsulfuric acids, lithium perchlorate, lithium tetrafluoroborate, acetyltriphenylphosphonium bromide, zirconium hydre, potassium cyanide and platinum e. Preferred catalysts include sulfonic acids, Lewis acids, polyvinylpyridines, methanesulfonic acid, AMBERYLST® 15, acid versions of DOWEX® and pyridinium p-toluenesulfonate (PPTS) with polyvinylpyridines, pyridinium p-toluensulfonate (PPTS), DOWEX® AMBERYLST® 15 and methanesulfonic acid, being most preferred. Catalyst mixtures are also within the scope of the present invention. Similarly, uses of supported catalysts, such as in a column for a continuous reaction and unsupported catalysts are also within the scope of the present invention. The catalysts are preferably used in amounts of from about 0.1 mole% to about 20.0 mole%, most preferably from about 0.1 mole%, to about 10.0 mole%, most preferably still from about 0.1 mole% to about 5.0 mole%, very preferably still about 0.1 mol% to about 2.0 mol%, most preferably still from about 0.2 mol% to about 1.0 mol%. Other catalysts . .. > Suitable biolics can be found in the US patent. No. 4,272,394 and in PCT publications WO 94/22800, WO 93/04153, WO96 / 00253 and WO 98/17379 all of which are incorporated herein by reference. In one embodiment of this aspect of the invention, the reaction is conducted in the presence of a solvent or solvent mixtures. It is preferred that the solvent be a polar aprotic solvent. Such solvents include, but are not limited to, hexane, benzene, toluene, xylene, mesitylene, dichloromethane, tetrahydrofuran, dioxane, diethyl ether, methyl tertiary butyl ether, acetone, acrylonitrile, or the like. In addition, the reaction is preferably conducted at temperatures of from about -20 ° C to about 300 ° C, and most preferably from about -10 ° C to about 250 ° C. Finally, the reaction is preferably conducted at pressures ranging from about 0.5 atmospheres to about 100 atmospheres, and most preferably from about 0.8 atmospheres to about 10 atmospheres. In another embodiment of this aspect of the present invention, the step of reacting vinyl ether with alkoxylated alcohol is conducted in the absence of a solvent. A further description of suitable solvents and catalysts can be found in "Advanced Organic Chemistry," by Jerry March, 4th ed., Wiley-lnerscience, 1992, "Comprehensive Organic Transformations" by Richard C. Larock, VCH Publishers, 1989, and " Protective Groups in Organic Synthesis "3rd ed., By Theodora W. Grene and Peter GM Wuts, Wiley-lnterscience, 1999, whose relevant portions are incorporated herein by reference. In one embodiment of the present invention, the method is performed as an intermittent procedure. That is, the reaction is allowed to proceed until complete, or almost to completion, and then the final product is removed. In another embodiment of the present invention, the method is carried out as a continuous process. That is, the product of the process is continuously removed from the reaction vessel while the starting material is added at a comparable rate. In one embodiment of the present invention, the vinyl ether is reacted with the alkoxylated alcohol at a molar ratio of from about 5 to about 1, most preferably from about 3 to about 1, most preferably still from about 1.5: 1 to apprately 0.90: 1 molar%. In one embodiment of the method of the present invention, the process can be conducted in an inert gas. This can be done using any inert gas such as nitrogen, helium, neon or argon. In one embodiment of the present invention, the reaction step (c) can be followed by the additional step (d). Step (d) is a step from which the reaction step (c) is quenched, preferably by the addition of a base. The amount of poly (oxyalkylated alcohol) surfactant blocked with ether present in the reaction mixture will depend on its factors, including but not limited to starting materials, temperature, selection of catalyst and the like. Extinction stops the reaction of the starting materials and ensures that any poly (oxyalkylated alcohol) surfactant blocked with ether produced does not undergo additional reaction or revert to the starting materials. The extinction of step (c) produces a mixture containing poly (oxyalkylated alcohol) surfactant blocked with ether, as well as unreacted starting materials, catalyst and the products of any side reactions. In one embodiment of this invention, quenching the reaction of step (c) is done when the reaction mixture preferably contains at least 90%, most preferably 95% by weight of poly (oxyalkylated alcohol) surfactant blocked with ether. The remaining 10%, most preferably 5% by weight, comprises unreacted starting material as well as products of side reactions such as acetal byproducts. In one aspect of this embodiment of the present invention, the base can optionally be selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal hydroxides, alkali metal alcolates, alkanolamines, alkylamines, aromatic amines and mixtures thereof. In a further aspect of the present invention, the base can optionally be selected from the group consisting of potassium carbonate, sodium carbonate, sodium bicarbonate, sodium methoxylate, sodium ethoxylate, potassium tert-butyloxylate, triethylamine, triethanolamine and mixtures thereof. In another aspect of this embodiment of the present invention, the base may be in the form of an aqueous solution. In a further aspect of this embodiment of the present invention, the aqueous solution may be at a temperature of from about 20 ° C to about 60 ° C. The term "product of step (c)" means that it includes not only the poly (oxyalkylated alcohol) surfactant blocked with ether, it blocks any unreacted starting materials or any materials produced from side reactions such as dimers, which would be present at the end of step (c). In one embodiment of the present invention, the method of the present invention may optionally further comprise a step (e). Step (e) is the removal of colored bodies and / or smells from the product of steps (c) or (d). In one aspect of this embodiment of the present invention, the removal of the color bodies and / or odors is obtained by contacting the product of steps (c) or (d) with a reagent. The reagent can be either an oxidant or a reductant. Suitable oxidants include hydrogen peroxide. Suitable reductants include sodium borohydride, and hydrogen on a palladium / carbon catalyst. In a further aspect of this embodiment of the present invention, the color bodies and / or odors are removed by contacting the product of steps (c) and (d) first with an antioxidant and then a reducing agent or first with a reducing agent and then an oxidant. In one embodiment of the present invention, the ether-blocked poly (alkylated) alcohol surfactant produced in step (c) can be optionally removed from the product of steps (c) or (d) by centrifuging. Some representative examples of this synthesis route of this aspect of the invention are demonstrated by the following diagrams.
The poly (oxyalkylated alcohol) surfactant product blocked with ether is then collected by means common in the art such as extraction. If desired, the surfactant can be further treated by separation, distillation, or other means before use. The surfactants made by the process described herein may contain related impurities that will not adversely affect performance.
Co-aminating Amine Oxide Surfactant In one aspect of the present invention, the composition of the present invention in addition to the poly (oxyalkylated alcohol) surfactant blocked with ether contains a co-surfactant of ^ fgU jÜ ^ amine oxide. The amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides typically containing an alkyl portion of from about 8 to about 22 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups which they contain from about 1 to about 3 carbon atoms. In one embodiment of this aspect of the present invention, suitable amine oxide surfactants can be selected from those of the formula: Wherein R3 is a linear or branched alkyl, linear or branched hydroxyalkyl or a linear or branched alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 1 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3 and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be linked to one another, for example, through an oxygen or nitrogen atom to form a ring structure. i? * ^ AU e *.
In one embodiment of this aspect of the present invention, suitable amine oxide surfactants in particular include C 1 or C 8 alkyldimethylamine oxides and C 8 -C 12 alkoxy ethyldihydroxyethylamine oxides. In one embodiment of this aspect of the present invention, suitable amine oxide surfactants in particular include a mixture of amine oxides with a resulting mixture having an average carbon content (branched or linear) for R3 of 16/17. . In one embodiment of this aspect of the present invention, the amine oxide surfactants will be made from natural products. For example, isostearyl. In another embodiment of this aspect of the present invention, the suitable amine oxide surfactants will be completely synthetic. Mixtures of amine oxides made from natural products and synthetic materials are also within the scope of the present invention. Suitable amine oxides can be produced by any conventional synthesis method. For example, they can be produced from alpha olefin or alcohol directly. Suitable amine oxide surfactants include, but are not limited to, hexadecylbis (2-hydroxyethyl) amine oxide, tallowbis (2-hydroxyethyl) amine oxide, stearylbis (2-hydroxyethyl) amine oxide, hexadecyldimethylamine oxide, of oleibis (2-hydroxyethyl) amine, dodecyldimethylamine oxide, tetradecyldimethylamine oxide dihydrate and mixtures thereof.
For further examples of suitable amine oxide surfactants see patents of E.U.A. 5,075,501 and 5,071, 594, incorporated herein by reference. The highly preferred amine oxides herein are solutions at room temperature. Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo chemie, Ethyl Corp., and Procter & Gamble. See the McCutcheon compilation and the Kirk-Othmer review article for alternative amine oxide manufacturers. In one embodiment of this aspect of the present invention, the amine oxide is present in the composition in an effective amount, most preferably from about 0.1% to about 20%, most preferably still from about 0.1% to about 15%, most preferably still from about 0.3% to about 10% by weight. Examples of suitable amine oxide surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II of Schwartz, Perry and Berch).
Auxiliary Ingredients and Methods In general, a cleaning aid is any material required to transform a composition containing only the minimum essential ingredients into a composition useful for cleaning purposes, such as cleaning fabrics, cleaning table linen, cleaning surfaces hard or personal cleansing (such as body wash or shampoo). • * &awBS ^ In addition, the surfactants of the present invention are also useful in post-wash cycle compositions, such as in fabric softeners and antistatic compositions. In the preferred embodiments, cleaning aids are easily recognizable by those skilled in the art, as absolutely characteristic of cleaning products, especially cleaning products intended for direct use by a consumer in a domestic environment. Bleaching auxiliaries are those auxiliaries which are preferably compatible with bleach or bleach stable. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition of the nature of the cleaning operation for which it is to be used. Preferably, the auxiliary ingredients, if used with bleach, should have good stability therewith. Certain preferred detergent compositions herein must be boron-free and / or phosphate-free as required by law. The levels of auxiliaries are from about 0.00001% to about 99.9% by weight of the compositions. The levels of use of the general compositions can vary widely depending on the intended application, varying for example from a few ppm in solution to the so-called "direct application" of the net cleaning composition to the surface to be cleaned.
Common auxiliaries include detergency builders, co-surfactants, enzymes, polymers, bleaches, bleach activators, catalytic materials and the like excluding any materials already defined above as part of the essential component of the compositions of the invention. Another auxiliary herein may include various active ingredients or specialized materials. For example, dispersing polymers (eg, from BASF Corp. or Rohm &Haas), colored speckles, silver care agents, anti-rust and / or anti-corrosion, colorants, fillers, germicides, bactericides, sources of alkalinity, hydrotropes, anti-oxidants, enzyme stabilizing agents, foam enhancers, pH regulators, anti-fungal agents, mildew control agents, insect repellents, anti-corrosive auxiliaries, chelators, foam suppressors, thickeners, abrasives, pro -perfumes, perfumes, solubilizing agents, vehicles, processing aids, pigments and for liquid formulations, solvents as described in detail below.
Co-surfactants The compositions according to the present invention may further comprise additional surfactants, hereinafter referred to as co-surfactants, preferably selected from anionic surfactants, preferably selected from surfactants of oxylated alkyl sulphates, alkyl sulphates, alkyldisulfates and /or t. S, Ir ?, linear alkylbenzene sulfonate; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglycosides, polyhydroxy fatty acid amides and / or amine or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and / or polycarboxylates (for example polyglycinates); and zwitterionic surfactants. A range of these co-surfactants can be used in the cleaning compositions of the present invention. A typical list of the anionic, nonionic, ampholytic and suteryonic classes, and species of these surfactant coagents, is given in the U.S. patent. 3,664,961 issued to Norris on May 23, 1972. Amphoteric surfactants are also described in detail in "Amphoteric Surfactants, Second Edition", E.G. Lomax, Editor (published in 1996 by Marcel Dekker, Inc.). Suitable surfactants can be found in the patent applications of E.U.A. series Nos. 60 / 032,035 (Case No. 6401 P), 60/031, 845 (Case No. 6402P), 60/031, 916 (Case No. 6403P), 60/031, 917 (Case No. 6404P), 60/031, 761 (Case No. 6405P), 60/031, 762 (Case No. 6406P), 60/031, 844 (Case No. 5409P), No. 60/061, 971, Proxy case no. 5881 P October 14, 1997, No. 60/061, 975, Proxy Case No. 6882P October 14, 1997, No. 60 / 062,086, Proxy Case No. 5883P October 14, 1997, No. 60/061, 916 , Proxy Case No. 6884P October 14, 1997, No. 60/061, 970, Proxy Case No. 6885P October 14, 1997, No. 60 / 062,407, Proxy Case No. 6886P October 14, 1997, 60 / 053,319 filed on July 21, 1997 (Case No. 6766P), 60 / 053,318 filed on July 21, 1997 (Case No. 6767P), 60 / 053,321 filed on July 21, 1997 (Case No. 6768P), 60 / 053,209 filed on July 21, 1997 (Case No. 6769P), 60 / 053,328 filed on July 21, 1997 (Case No. 6770P), 60 / 053,186 filed on July 21, 1997 (Case No. 6771 P) , 60 / 053,437 filed on August 8, 1997 (Case No. 6796P), 60 / 105,017 filed on October 20, 1998 (Case No. 7303P), and 60 / 104,962 filed on October 20, 1998 (Case No. 7304P) all of which are incorporated herein by reference. The compositions of the present invention preferably comprise from about 0.01% to about 55%, most preferably from about 0.1% to about 45%, most preferably from about 0.25% to about 30%, most preferably about 0.5% a about 20% by weight co-surfactants. The co-surfactants are further identified in the following manner. (1) Anionic surfactant co-surfactants Non-limiting examples of anionic co-surfactants useful herein, typically at levels of from about 0.1% to about 50% by weight, include the conventional alkylbenzene sulfonates ("LAS") of Cn-C Β8 and C10-C20 primary, branched-chain and random alkylsulfates ("AS"), the secondary alkyl sulfates (2.3) of C10-C-iß of the formula CH3 (CH2x (CHOSO3"M +) CH3 and CH3 ( CH2) and (CHOSO3 ~ M +) CH2CH3 where xy (y + 1) are integers of at least about 7, preferably at least about 9, and M is a cation soluble in water, especially sodium, unsaturated sulfates such as oleyl sulfate , the alpha-sulfonated fatty acid esters of C10-C18, the sulfated alkyl polyglycosides of C10-C? 8, the alkylalkoxy sulfates of C10-C? ß ("AEXS", especially EO 1-7 ethoxysulfates), and C10-C18 alkylalkoxycarboxylates (especially EO 1-5 ethoxycarboxylates) Betaines and sulfobetaines of C12-C18 ("sultaines"), C10-C18 amine oxides, and the like, may also be included in the general compositions. Conventional C? O-C2o soaps can also be used- If high foaming is desired, branched-chain C10-C16 soaps can be used. Other conventional useful anionic surfactant coagents are listed in standard texts. Other suitable anionic surfactants that can be used are alkyl ether sulfonate surfactants including C8-C20 carboxylic esters (ie, fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society". 52 (1975), pp. 323-329. Suitable starting materials will include natural acid substances as derived from bait, palm oil, etc. Another type of useful surfactants are the so-called dianionics. These are surfactants having at least two anionic groups present in the surfactant molecule. Some suitable anionic surfactants are further described in the application of E.U.A. co-pending series No. 60 / 020,503 (Case No. 6160P), 60 / 020,772 (Case No. 6161 P), 60 / 020,928 (Case No. 6158P), 60 / 020,832 (Case No. 6159P) and 60 / 020,773 (Case No. 6162P) all filed on June 28, 1996 and 60 / 023,539 (Case No. 5192P), 60/023493 (Case No. 6194P), 60/023540 (Case No. 6193P) and 60 / 023,527 (Case No. 6195P) filed on August 8, 1996, the descriptions of which are incorporated herein by reference. In addition and preferably, the surfactant may be a branched alkyl sulfate, branched alkylalkoxy or branched alkoxylated alkylsulfate. These surfactants are also described in No. 60/061, 971, case of proxy No. 6881 P, October 14, 1997, No. 60/061, 975, case of attorney No. 6882P, October 14, 1997, No. 60 / 062,086, attorney-in-fact case No. 6883P, October 14, 1997, No. 60/061, 916, attorney-in-fact case No. 6884P, October 14, 1997, No. 60/061, 970, case of attorney-in-fact No. 6885P, October 14, 1997, No. 60 / 062,407, attorney-in-fact case No. 5886P, October 14, 1997. Other suitable branched-chain surfactants in the middle of the chain can be found in the patent application of USA series No. 60 / 032,035 (Case No. 6401 P), 60/031, 845 (Case No. 6402P), 60/031, 916 (Case No. 6403P), 60/031, 917 (Case No. 6404P), 60/031, 761 (Case No. 6405P), 60/031, 762 (Case No. 6406P) and 60/031, 844 (Case No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions. In addition, the surfactant can be a modified alkyl benzene sulfonate surfactant or MLAS. MLAS surfactants can be found in the US patent. series Nos. 60 / 053,319 filed on July 21, 1997 (Case No. 6766P), 60 / 053,318 filed on July 21, 1997 (Case No. 6767P), 60 / 053,321 filed on July 21, 1997 (Case No 6768P), 60 / 053,209 filed on July 21, 1997 (Case No. 6769P), 60 / 053,328 filed on July 21, 1997 (Case No. 6770P), 60 / 053,186 filed on July 21, 1997 (Case No. 6771 P), 60 / 053,437 filed on August 8, 1997 (Case No. 6796P), 60 / 105,017 filed on October 20, 1998 (Case No. 7303P), and 60 / 104,962 filed on October 20, 1998 (Case No. 7304P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions. The anionic surfactants useful in the LDL of the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonate, alpha-olefin sulfonate, paraffinsulfonates, alkyl ether sulfonates, alkyl sulfates, alkylalkoxysulfate, alkylsulfonates, alkylalkoxycarboxylate, alkoxylated alkylsulfates, sarcoxinates, taorinates and mixtures thereof. An effective amount, typically about 0.5% to about 90%, preferably about 5% a & . i &fcfc-Jt: - i: i ~ i about 50%, most preferably from about 10% to about 30% by weight of anionic detersive surfactant can be used in the LDL compositions of the present invention. When included in these, the laundry detergent compositions of the present invention typically comprise from about 0.1% to about 50%, preferably from about 1% to about 40% by weight of an anionic surfactant. (2) Nonionic surfactant coagents Non-limiting examples of nonionic surfactant coagents useful herein typically at levels of from about 0.1% to about 50% by weight include alkoxylated alcohols (AE) and alkylphenols, polyhydroxy fatty acid amides ( PFAA), alkyl polyglucosides (APG), glycerol esters of C10-C18 and the like. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the condensation product of linear secondary alcohol of C 11 -C 15 with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMW ( the condensation product of C12-C14 primary alcohol of 6 moles of ethylene oxide with a narrow molecular weight solution), both marketed by Union Carbide Corporation; Neodol ™ 45-9 (the linear condensation product of C14-C15 with 9 moles of ethylene oxide), Neodol ™ 23-3 (the linear C12-C13 alcohol condensation product with 3 moles of ethylene oxide ), Neodol ™ 45-7 (the linear condensation product of C14-C15 with 7 moles of ethylene oxide), Neodol ™ 45-5 (the linear alcohol condensation product d4- C15 with 5 moles of ethylene), marketed by Shell Chemical Company; Kyro ™ EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & gamble Company; and Genapol LA 030 or O5O (the condensation product of C 2 -Cl 4 alcohol with 3 or 5 moles of ethylene oxide), marketed by Hoechst.
The preferred HLB range in these nonionic surfactants of AE is 8-17 and more preferred is 8-14. Condensates with propylene oxide and butylene oxides can also be used. Another class of nonionic surfactant coagents that are preferred to be used herein are the polyhydroxy fatty acid amide surfactants of the formula: wherein R is H, or C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is C5-31 hydrocarbyl and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydrocarbyl. hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Typical examples include N-methylglucamides of C12-Ciß and C12-C14. See E.U.A. 5,194,639 and 5,298,636. The N-alkoxy polyhydroxy fatty acid amides can also be used; see E.U.A. 5,489,393.
Also useful as a nonionic surfactant coagent in the present invention are alkylpolysaccharides such as those described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986. Preferred alkyl polyglycosides have the formula R2O (CnH2nO) t (glucosyl)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glucosyl is preferably derived from glucose. To prepare these compounds, the alkylpolyethoxylated alcohol or alcohol is first formed, and then reacted with glucose or a source of glucose to form the glucoside (attachment at position 1). The additional glucosyl units can then be fixed between their position 1 and position 2-, 3-, 4- and / or 6- of the preceding glucosyl units, preferably and predominantly position 2. Compounds of this type and their Use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118.
The polyethylene oxide, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being more preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in a straight chain or chain configuration branched with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to about 25 moles, most preferably about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ™ CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (for example, alkylphenol ethoxylates). The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The ^ ^ ¿^ J,. J ,, ^ ,, ^, ^. ,. "...,". s. -. ,. "-. If the addition of portions of polyoxethylene to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the of polyoxyethylene is about 50% of the total weight of the condensation product, which corresponds to the condensation to about 40 moles of ethylene oxide. Examples of compounds of this type include certain Pluronic ™ surfactants commercially available and sold by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of The condensation contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic ™ compounds, marketed by BASF. When the composition is an automatic dishwashing composition (ADW), it preferably contains co-agents ** Jí t nonionic surfactants. In general, non-ionic co-surfactants stable to the bleach are preferred. When present, these nonionic surfactant coagents are included at levels of from about 0.1% to about 15% of the composition. The nonionic surfactant co-agent may be a low cloud point nonionic co-surfactant, a high cloud point nonionic co-surfactant or mixtures thereof. A preferred ADW composition of the present composition includes a low turbidity point nonionic co-surfactant and / or a high cloud point nonionic co-surfactant in addition to the surfactant of the present invention. Nonionic surfactants are generally well known, described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3a. ed., vol. 22, pp. 360-379, "Surfactants and Detersive Systems", listed here by reference. As used herein, "cloud point" is a well-known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase it can be observed is referred to as the "turbidity point" (see Kirk Othmer, pp. 360-362, previously mentioned). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30 ° C, preferably less than about 20 ° C. C and very preferably* - * «-« * - less than approximately 10 ° C. Typical low cloud point co-surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Poly-Tergent® SLF18 from Olin Corporation) and poly (oxyalkylated) alcohols blocked with epoxy (e.g., Poly series). -Tergent® SLF18B by Olin Corporation of nonionic surfactants, as described for example in WO 94/22800, published on October 13, 1994 by Olin Corporation). The nonionic co-surfactants may optionally contain propylene oxide in an amount of up to 15% by weight.
Other preferred nonionic surfactants can be prepared by the methods described in the U.S.A. 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference. The low cloud point nonionic co-surfactants further comprise a polymeric polyoxyethylene-polyoxypropylene block compound. The polyoxyethylene-polyoxypropylene block polymer compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylene diamine as the reactive hydrogen compound of initiator. Some of the agent compounds . l Ál »t i .. block polymer surfactant designated as PLURONIC®, REVERSED PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.
Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702. Said surfactant co-agents are typically used herein as non-low cloud point surfactants. As used herein, a "high cloud point" nonionic co-surfactant is defined herein as a nonionic surfactant system ingredient having a cloud point greater than 40 ° C, preferably greater than about 50 ° C. ° C, and most preferably greater than about 60 ° C. Preferably, the nonionic co-surfactant co-surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydric alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with an amount of from about 6 to about 15 moles. of ethylene oxide per mole of alcohol or alkylphenol on an average basis. Such high cloud point nonionic co-surfactants include, for example, Tergitol 15S9 (provided by Union Carbide), Rhodasurf TMD 8.5 (provided by Rhone Poulenc), and Neodol 91-8 (provided by Shell). It is also preferred for purposes of the present invention that the high cloud point nonionic co-surfactant also has an equilibrium equilibrium equilibrium value ("HLB", see Kirk Othmer below) within of the interval of about 9 to 1 1 about 15, preferably from 11 to 15. Such materials include, for example, Tergitol 15S9 (provided by Union Carbide), Rhodasurf TMD 8.5 (provided by Rhone Poulenc), and Neodol 91-8 (provided by Shell). Another preferred high cloud point nonionic surfactant co-agent is derived from a straight chain or preferably branched or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (C6-C20 alcohol). including secondary alcohols and branched chain primary alcohols. Preferably, the high cloud point nonionic co-surfactants are branched or secondary ethoxylated alcohols, most preferably branched Cg / non-Cu / 15 branched ethoxylated alcohols, condensed with an average of about 6 to about 15 moles, preferably around 6 to about 12 moles, and most preferably from about 6 to about 9 moles of ethylene oxide per mole of alcohol. Preferably the ethoxylated nonionic co-surfactant derived in this manner has a narrow ethoxylate distribution in relation to the average. When the optional surfactant co-agents are a mixture of low cloud point and high cloud point nonionic surfactants, it is preferred that the blend be combined in a weight ratio preferably within the range of about 10: 1 to approximately 1: 10. (3) Cationic surfactant coagents Non-limiting examples of cationic surfactant coagents useful herein typically at levels of from about 0.1% to about 50% by weight, include the choline ester quaternary and the alkoxylated quaternary ammonium surfactant compounds (AQA ), and the like. Most preferred for aqueous liquid compositions of the present invention are soluble cationic co-surfactants which are not readily hydrolyzed in the product. The cationic surfactant coagents useful as a component of the surfactant system is a quaternary surfactant of the cationic choline ester type which are preferably water dispersible compounds having surfactant properties and comprising at least one ester linkage (i.e. -COO-) and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, are described, for example, in U.S. Patents. Nos. 4,228,042, 4,239,660 and 4,260,529. Preferred cationic ester surfactants are those having the formula: wherein R ^ is an alkyl, alkenyl or alkaryl chain of C5-C3? linear or branched or M ".N + (R6R7R8) (CH2) S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO whereby at less one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R2, R3, R4, R6, R7 and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms, and R5 is independently H or a C1-C3 alkyl group, wherein the values of m, n, syt are independently on the scale from 0 to 8, the value of b is found in the scale from 0 to 20, and the values of a, u and v are independently either 0 or 1, with the proviso that at least one of uov is 1, and where M is a counter anion, preferably R2, R3 and R 4 are independently selected from CH 3 and -CH 2 CH 2 OH Preferably, M is selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, most preferably between methyl sulfate, chloride, bromide or iodide. Preferred water-dispersible cationic ester surfactants are choline esters having the formula: i? rá. ^ 2s? a ..- to JJHA, », I where Ri is a linear or branched C11-C19 alkyl chain. Particularly preferred choline esters of this type include the quaternary methylammonium halides of stearoyl choline ester (R1 = C17 alkyl), the quaternary methylammonium halides of palmitoylcholine ester (R1 = C15 alkyl), the quaternary mephilamonium halides. of myristoylcholine ester (R1 = C13 alkyl), quaternary mephilamonium halides of lauroylcholine ester (R1 = Cu alkyl), quaternary methylammonium halides of cocoylcholine ester (R1 = C11-C13 alkyl), halides of quaternary methylammonium seboylcholine ester (R1 = C15-C17 alkyl) and any mixture thereof. Particularly preferred and above-mentioned choline esters can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, water, propylene glycol or preferably an ethoxylated fatty alcohol such as ethoxylated C 10 -C 18 fatty alcohol having a degree of ethoxylation of 3 to 50 ethoxy groups per mole forming the desired cationic material. They can also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is subsequently quaternized with trimethylamine, forming the desired cationic material.
In a preferred aspect, these cationic ester surfactants are hydrolysable under the conditions of a laundry method. Cationic surfactant coagents useful herein also include the alkoxylated quaternary ammonium surfactant compounds (AQA) (hereinafter referred to as "AQA compounds") having the formula: wherein R1 is a linear or branched alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, more preferably about 10 to about 14 carbon atoms; R2 is an alkyl group containing one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X- is an anion such as chloride, bromide, methylisulfate, sulfate or the like, sufficient to provide electrical neutrality. A and A 'can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and ethoxy / propoxy mixed; p is from 0 to about 30, preferably 1 to about 4 and q is from 0 to about 30, preferably 1 to about 4 and more - ,. ... to. a t a to preferably about 4; preferably p and q are 1. See also: EP 2,084, published May 30, 1979 by The Procter & Gamble Company, which discloses cationic surfactant coagents of this type that are also useful herein. The levels of AQA surfactants used to prepare the finished laundry detergent compositions can vary from about 0.1% to about 5%, typically from about 0.45% to about 2.5% by weight.
Aqueous liquid vehicle The auxiliary rinsing compositions herein contain in addition to about%% to?% Of an aqueous liquid vehicle in which the other components of essential and optional compositions are dissolved, dispersed or suspended. Most preferably, the aqueous liquid carrier will comprise from about% to% of the compositions of the present invention. An essential component of the aqueous liquid vehicle is, of course, water. However, the aqueous liquid vehicle may contain other materials which are liquid or which dissolve in the liquid vehicle at room temperature and which may also have some other function in addition to that of a simple filler. Such materials may include, for example, hydrotropes and solvents. Due in large part to the properties of the branched surfactant agents in the middle of the chain of the present invention, the water in the aqueous liquid carrier can have a hardness level of at least about 15 gpg or more ("gpg" is a water hardness measurement that is well known to those skilled in the art and represents "grains per 3.78 liters"). A variety of water immiscible liquids such as lower alcohols, diols, other polyols, ethers, amines and the like can be used as part of the aqueous liquid carrier. Particularly preferred are C1-C4 alcohols. Said solvents may be present in the compositions of the present invention to a degree of about?% To?%.
Polymeric Foam Stabilizer The compositions of the present invention may optionally contain a polymeric foamer stabilizer. These polymeric foam stabilizers provide extended foam volume and extended foam life without sacrificing the fat-cutting ability of liquid detergent compositions. These polymeric foam stabilizers are selected from: i) homopolymers of (N, N-dialkylamino) alkyl acrylate esters having the formula: wherein each R is independently hydrogen, d-Cß alkyl, and mixtures thereof, R 1 is hydrogen, C Cß alkyl, and mixtures thereof, n is from 2 to about 6; and ii) copolymers of (i) and wherein R1 is hydrogen, Ci-Cß alkyl and mixtures thereof, provided that the ratio of (ii) to (i) is from about 2 to 1 to about 1 to 2; The molecular weight of the polymeric foaming enhancers, determined by conventional gel penetration chromatography, is from about 1,000 to about 2,000,000, preferably from about 5,000 to about 1,000,000, most preferably from about 10,000 to about 750,000. , most preferably from about 20,000 to about 500,000, most preferably still from about 35,000 to about 200,000. The polymeric foam stabilizer may optionally be present in the form of a salt, either an inorganic or organic salt, for example the (N, N-dimethylamino) alkyl acrylate ester citrate, sulfate or nitrate salt. A preferred polymeric foam stabilizer is (N, N-dimethylamino) alkyl acrylate ester; namely • - • - - «« * • «-« * * When present in the compositions, the polymeric foaming enhancer may be present in the composition from about 0.01% to about 15%, preferably from about 0.05% to about 10%, most preferably from about 0.1% to about 5% by weight. Other suitable polymeric foam stabilizers, including proteaseous foam stabilizers and switerionic foam stabilizers, can be found in PCT / US98 / 24853, filed November 20, 1998 (case No. 6938), PCT / US98 / 24707 filed 20 of November 1998 (case No. 6939), PCT / US98 / 24699 filed on November 20, 1998 (case No. 6943), and PCT / US98 / 24852 filed on November 20, 1998 (case No. 6944). Also suitable are the cathonic copolymer stabilizers, which can be found in the US patent. 4454060.
Enzymes The detergent compositions of the present invention may further comprise one or more enzymes that provide cleaning performance benefits. Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, glucoamylase, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases or mixtures thereof. A combination Preferred% is a detergent composition having a mixture of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase. The enzymes, when present in the compositions, are between about 0.0001% and about 5% active enzyme by weight of the detergent composition.
Proteolytic Enzyme The proteolytic enzyme can be of animal, vegetable or microorganism origin (preferred). Proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-like proteases. Preferred to be used herein are proteolytic enzymes of the subtilisin type. Particularly preferred is a bacterial serine proteolytic enzyme obtained from β. subtilis and B. licheniformis. Suitable proteolytic enzymes include Alcalase® (preferred), Esperase® and Savinase® from Novo Industri A / S (Copenhagen, Denmark), Gist-brocades' and Maxatase®, Maxacal® and Maxapem 15® (Maxacal® treated by protein genetic engineering techniques) (Delft, The Netherlands), and BPN and BPN subtilisins (preferred), which are commercially available. Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genecor International, Inc. (San Francisco, California) which are described in European Patent No. 251,446B, issued December 28, 1994 . . , i a a (particularly pages 17, 24 and 98) and which is called here "Protease B", and in the patent of E.U.A. 5,503,378, Venegas, issued July 9, 1991, which refers to a modified bacterial serine proteolytic enzyme (Genecor International) which is referred to herein as "Protease A" (the same as BPN '). In particular, see columns 2 and 3 of the US patent. 5,030,378 for a complete description, including amino acid sequence, of protease A and its variants. Other proteases are sold under the trade names: Primase, Durazym, Opticlean and Optimase. The preferred proteolytic enzymes are selected from the group consisting of Alcalase® (Novo Industri A / S), Protease A and Protease B (Genecor), and mixtures thereof, Protease B is the most preferred. Of particular interest for use herein are the proteases described in the U.S. patent. No. 5,470,733. Also, the proteases described in copending application USSN 08 / 136,797 can be included in the detergent composition of the invention. Another preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid with a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, + 123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274 in accordance with the subtilisin numbering of Bacillus amyloliquefaciens, as described in WO 95/10591 published on April 20, 1995 by Genecor International (A. Baeck et al. entitled "Protease-Containing Cleaning Compositions" which has the serial number of USA 08 / 322,676 , presented on October 13, 1994). Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1992 by The Procter & amp; amp;; Gamble Company; WO 95/30011 published November 9, 1992 by The Procter & Gamble Company; WO 95/29979 published November 9, 1992 by The Procter & Gamble Company. Protease enzymes can be incorporated according to the present invention at a level of 0.0001% to 2% active enzyme by weight of the composition.
Amylase Amylases (alpha and / or beta) can be included for the removal of carbohydrate-based stains. The suitable amylases are Termamyl® (Novo Nordisk), FungamylR and BAN ^ (Novo Nordisk). The enzymes can be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. Amylase enzymes are incorporated normally iüi L -í 4, * - t ^ i? .. in the detergent composition at levels from 0.0001% to 2%, preferably from about 0.0001% to about 5%, most preferably from about 0.0005% to about 0.1%, most preferably still from about 0.001% to about 0.05% enzyme Active in weight of the detergent composition. Amylase enzymes also include those described in W095 / 26397 and in the co-pending application of Novo Nordisk PCT / DK96 / 00056. A suitable amylase enzyme is NATALASE® available from Novo Nordisk. Other amylases suitable herein include, for example, the α-amylases described in GB 1, 296, 839 to Novo; RAPIDASE ^, International Bio-Synthetics, Inc. and TERMAMYLR, NOVO. FUNGAMYL from Novo is especially useful. Particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and are available from the Novo transferee, such as DURAMYL®. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example that derived by site-directed mutagenesis of chimeric, hybrid or simple known mutant progenitor forms of available amylases. They are also i rl -i.mi.a.? ¿. -liairr? . - .. .. ... í., - -,. . . ... . . j. *, -. n ", ... -., _ »... mt. "». . my. .. »» A * .ÍI accessible other modifications of enzyme that are preferred. See WO 9509909 to Novo. Several carbohydrase enzymes that impart antimicrobial activity may also be included in the present invention. Such enzymes include endoglycosidase, endoglycosidase type II and glucosidase are described in the patents Nos. 5,041, 236, 5,395,541, 5,238,834 and 5,356,803, the descriptions of which are incorporated herein by reference. Of course, other enzymes having antimicrobial activity can also be employed. peroxidases, oxidases and some other enzymes. The peroxidase enzymes can be used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc., Typically they are used for "bleaching in solution" or to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known and include, for example, horseradish peroxidase, ligninase and haloperoxidases such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described in the PCT International Application WO 89/099813, published October 19, 1989 by O. Kirk, assigned to Novo Industries A / S. The present invention includes peroxidase-free tableware automatic washing composition modalities. A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are described in patent of E.U.A. 3,553,139, issued on January 5, 1971 to McCarty. In addition, enzymes are described in the U.S.A. 4,101, 457, Place et al., Issued July 18, 1978 and in the patent of E.U.A. 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. patent. 3,600,319, issued August 17, 1971 to Gedge et al., And EP 0 199,405 and application No. 86,200,586.5, published October 29, 1986., Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570. Enzymes can be incorporated in detergent compositions herein in the form of suspensions, "marumes" or "pills". Another suitable type of enzymes comprises those in the form of enzyme suspensions in nonionic surfactants, for example, enzymes marketed by Novo Nordisk under the tradename "SL" or microencapsulated enzymes marketed by Novo Nordisk under the tradename "LDP" . Enzymes added to the compositions herein in the form of conventional enzyme pills are especially preferred for use in the present invention. Said pills will generally vary in size from about 100 to 1,000 microns, most preferably from about 200 to 800 microns and will be suspended during the non-aqueous liquid phase of the composition. The pills in the composition of the present invention have been found, in comparison with other forms of enzyme, to exhibit enzyme stability especially desirable in terms of retention of enzyme activity over time. In this manner, compositions using enzyme pills do not need to contain conventional enzyme stabilization as often should be used when the enzymes are incorporated in aqueous liquid detergents. If employed, the enzymes will normally be incorporated into the non-aqueous liquid compositions herein at levels sufficient to provide up to about 10 mg by weight, very typically from about 0.01 mg to about 5 mg, of active enzyme per gram of the composition . Stated otherwise, the non-aqueous liquid detergent compositions herein will typically comprise from about 0.001% to 5%, preferably from about 0.01% to 1% by weight of a commercial enzyme preparation. Protease enzymes, for example, are generally present in such commercial preparations at levels sufficient to provide 0.005 to 0J Anson units (AU) of activity per gram of composition.
Enzyme Stabilization System The compositions containing enzymes herein may also comprise from about 0.001% to about 10%, preferably about 0.005% to about 8%, most preferably about 0.01% to about 6% by weight of a AtJr t i Í..Í. i-? r.1 ... ? -i i. enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is compatible with the protease or other enzymes used in the compositions herein. Said enzyme stabilization systems may comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acid and mixtures thereof, and are designed to face different stabilization problems depending on the type and physical form of the composition. Detergent. 10 Perfumes The perfumes and perfumery ingredients useful in the present compositions and methods comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters and the like. Also included are several 15 extracts and natural essences which may comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar and the like. The finished perfumes can comprise extremely complex mixtures of said ingredients. The products Finishes typically comprise from about 0.01% to about 2% by weight of the detergent compositions herein, and the individual perfumery ingredients can comprise about 0.0001% to about 90% of a finished perfume composition.
Dispersing polymer 5 The compositions of the present invention may also contain a dispersant polymer. When present, a dispersant polymer in the present compositions is typically at levels in the range from 0 to about 25%, preferably from about 0.5% to about 20%, most preferably from about 1% to about 10 about 8% by weight of the composition. Dispersing polymers are useful for improved film performance of the present compositions, especially in higher pH embodiments, such as those in which the wash pH exceeds about 9.5. Particularly preferred are polymers which exhibit the deposition of 15 calcium carbonate or magnesium silicate on the tableware. Dispersing polymers suitable for use in the present invention are further illustrated by the film-forming polymers described in the U.S.A. DO NOT. 4,379,080 (Murphy), issued April 5, 1983. 20 Suitable polymers are preferably at least partially neutralized salts of alkali metal, ammonium or substituted ammonium (eg mono-, di or triethanolammonium) of polycarboxylic acids. Alkali metal salts, especially sodium, are most preferred. Although the The molecular weight of the polymer can vary over a wide range, preferably it is from about 1,000 to about 500,000, most preferably from about 1,000 to about 250,000 and most preferably, especially if the composition is to be used in North American automatic dishwashers, from about 1,000 to about 5,000. Other suitable dispersant polymers include those of the U.S.A. Nos. 3,308,067, 4,530,766, 3,723,322, 3,929,107, 3,803,285, 3,629,121, 4,141, 841 and 5,084,535; European Patent No. 66,915. The acrylamide and acrylate copolymers having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the dispersant polymer can also be used. Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. The low molecular weight polyacrylate dispersing polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use in the present invention has a molecular weight of about 3,500 and is the form completely ZSXgf? neutralized from the polymer comprising about 70% by weight of acrylic acid and about 30% by weight of methacrylic acid. Other dispersant polymers useful in the present invention include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Other dispersant polymers useful in the present invention include cellulose sulfate ethers such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate and hydroxypropyl cellulose sulfate. Sodium cellulose sulfate is the most preferred polymer in this group. Another group of acceptable dispersants are organic dispersant polymers such as polyaspartate.
Material Care Agents When the compositions of the present invention are automatic dishwashing compositions they may contain one or more materials care agents that are effective as corrosion inhibitors and / or anti-rusting aids. Said materials are preferred components of automatic dishwashing compositions especially in certain European countries where the use of electrodeposited nickel silver and sterling silver is comparatively common in household crockery, or when aluminum protection is a concern and the composition is low in silicate. In general, such materials care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, phials, mercaptans, fatty acid-aluminum salts and mixtures thereof. When present, said protective materials are preferably incoforated at low levels, for example from about 0.01% to about 5% of the composition. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from about 20 to about 50; Preferred paraffin oil is selected from predominantly branched C25-45 species with a cyclic to non-cyclic hydrocarbon ratio of about 32:68. A paraffin oil that meets these characteristics is sold by Wintershall, Saizbergen, Germany, under the trade name WINOG 70. In addition, the addition of low levels of bismuth nitrate (ie Bi (N03) 3) is also preferred. Other corrosion inhibiting compounds include benzotriazole and comparable compounds; mercaptans and thiols include thionaphthol and thioanthranol; and finely divided fatty acid aluminum salts, such as aluminum tristearate. The formulator will recognize that said materials will generally be used judiciously and in limited amounts to avoid any tendency to produce spots or films on the dishes or to compromise the bleaching action of the compositions. For this reason, mercaptan anti-rust agents that are very strongly reactive to bleaching and common fatty carboxylic acids that precipitate with calcium in particular are preferably avoided.
Guelating Agents 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 consisting of aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending to be limited 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 the washing solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediamine triacetates, nitrilotriacetates, ethylenediamonotetraproprionates, triethylenetetramine-hexacetates, diethylenetriaminepentaacetates and ethanololdiglicines, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. The aminophosphonates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions and -fe «iA -? x include etílendiaminotetrakis (methylene phosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer as described in the U.S.A. 4,704,223 issued November 3, 1987 to Hartman and Perkins. The compositions herein may also contain water-soluble salts (or acid form) of methylglycine-acetic acid (MGDA) as a chelator or co-builder. Similarly, so-called "weak" builders such as citrate can also be used as chelating agents. If used, these chelating agents should generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents should comprise from about 0.1% to about 3.0% by weight of said compositions. pH of the composition The surfactants of the present invention can be used in compositions that cover a wide range, from acids to basic and all shades between them. The compositions of the present invention may have a pH of 2 to 12. If the composition with a pH greater than 7 is not going to be effective, it preferably should contain a pH regulating agent capable of providing a generally more alkaline pH in the composition. and in dilute solutions, ie, from about 0.1% to 0.4% by weight of the aqueous solution of the composition. The value of pKa 10 of this pH regulating agent should be about 0.5 to 1.0 pH units below the desired pH value of the composition (determined as described above). Preferably, the pKa of the pH regulating agent should be from about 7 to about 10. Under these conditions, the pH regulating agent controls more effectively 15 the pH while using the minimum amount of it. Similarly, an acidic pH regulator system can be employed to maintain the pH of the compositions. The pH regulating agent may be an active detergent by itself, or it may be an organic or inorganic material of low molecular weight, Which is used in this composition only to maintain an alkaline pH. One type of preferred pH regulating agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as licina or amines of lower alcohols such as mono-, di- and ^^^ m ^ triethanolamine. Other preferred pH-regulating agents containing nitrogen are tri (hydroxymethyl) aminomethane (HOCH2) 3CNH3 (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino -2-methyl-1, 3-propanol, disodium glutamate, N-methyldiethanolamine, 1,2-diamino-propanol, N, N'-tetra-methyl-1,3-diamino-2-propanol, N, N- bis (2-hydroxyethyl) glycine (bicine) and N-tris (hydroxymethyl) methylglycine (tricine). Mixtures of any of the foregoing are also acceptable. Alkalinity sources / organic pH regulators include alkali metal carbonates and alkali metal Ifosphates, for example, sodium carbonate, sodium polyphosphate. Also suitable are organic acids such as citric acid, acetic acid and the like. For additional pH regulators see Me Cutcheon's EMULSIFIERS AND DETERGENTS, North American edition, 1997, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971 both incorporated herein by reference. A highly preferred group of pH regulators, especially in LDL compositions, are the diamines. Preferred organic diamines are those in which the pK1 and pK2 are in the range of about 8.0 to about 11.5, preferably in the range of about 8.4 to about 11, most preferably still about 8.6 to about 10.75. Preferred materials for performance and delivery considerations are 1, 3-bis (methylamino) -cyclohexane, 1.3 propane diamine (pK1 = 10.5; pK2 = 8.8), 1.6 hexane diamine (pK1 = 11, pK2 = 10), 1.3 pentane diamine (Dytek EP) (pK1 = 10.5, pK2 = 8.9), 2- I tá £ ^ -. jjfri methyl 1,5, pentanediamine (Dytek A) (pK1 = 11.2, pK2 = 10.0). Other preferred materials are the primary / primary diamines with alkylene spacers ranging from C4 to C8. In general, it is believed that primary diamines are preferred over secondary and tertiary diamines.
Definition of pK1 v pK2 As used herein, "pKal" and "pKa2" are amounts of a type collectively known to those skilled in the art as "pKa". pKa is used here in the same way as chemistry experts commonly know it. The values referred to can be obtained from the literature, such as from "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa can be obtained from the relevant company's literature, such as information provided by DuPont, a diamine supplier. More detailed information on pKa can be found in the patent application of E.U.A. No. 08 / 770,972, filed December 29, 1996 to Procter & Gamble (case of attorney No, 6459). Examples of preferred diamines include the following: dimethylaminopropylamine, 1,6-hexanediamine, 1,3 propanediamine, 2-methyl 1,5-pentanediamine, 1,3-pentanediamine, 1,3-diaminobutane, 1,2-bis (2-aminoethoxy) ethane , Isophorone diamine, 1,3-bis (methylamine) -cyclohexane and mixtures thereof. 8 - The pH regulator can be supplemented (ie, for improved sequestration in hard water) by other optional builder salts selected from non-phosphate builders known in the art, including the various borates, water-soluble alkali metal, ammonium or substituted ammonium hydroxy sulphonates, polyacetates and polycarboxylates. Alkali metal, especially sodium, salts of said materials are preferred. Organic non-phosphorus, water soluble alternative builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium salts; lithium, ammonium and substituted ammonium of ethylenediaminetetraacetic acid, nitrilotriacetic acid, tartrate monosuccinic acid, disuccinic tartrate acid, oxydisuccinic acid, carboxymethoxysuccinic acid, melific acid and sodium benzene polycarboxylate salts. If used, the pH regulating agent is present in the compositions of the invention at a level of from about 0.1% to about 15%, preferably from about 1% to 10%, most preferably from about 2% to 8% by weight of the composition. If the optional pH regulator used is a diamine, the compositions will preferably contain at least about 0.1%, most preferably at least about 0.2%, most preferably at least about 0.25%, most preferably still at least about 0.5% in weight of said diamine composition. The aj jt fcuá Ma éasfc & d fc * & amp; , *** * *. - + * • * &amp * av «- * # **** • - ^^. *. *. ", Composition will also preferably contain no more than about 15%, most preferably no more than about 10%, most preferably not more than about 6%, most preferably not more than about 5%, most preferably not more than about 1.5 % by weight of said diamine composition.
Water-soluble silicates The present compositions may also comprise water-soluble silicates. The water-soluble silicates of the present invention are any silicates that are soluble to the extent that they do not adversely affect the stain / film removal characteristics of the composition. Examples of silicates are sodium methylsalicylate and, very generally, alkali metal silicates, particularly those having a Si 2: Na 2+ ratio. in the range of 1.6: 1 to 3.2: 1; and layered silicates, such as the layered sodium silicates described in the U.S.A. 4, 664,839, issued May 12, 1987 to H.P. Rieck NaSKS-6® is a crystalline layered silicate marketed by Hoechst (commonly abbreviated here as "SKS-6"). Unlike zeolite builders, NaSKS-6 and other water-soluble silicates useful herein do not contain aluminum. NaSKS-6 is the form of d-Na2S? S of layered silicate and can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043 of Germany. SKS-6 is a preferred layered silicate for use herein, but other layered silicates of this type, such as those having the general formula NaMSi? 02x +? and H20 where 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. Some other Hoechst stratified silicates include NaSKS-5, NaSKS-7 and NaSKS-11, as the a-, β- and β forms. Other silicates may also be useful, such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches and as a component of foam control system. Silicates particularly useful in automatic dishwashing (ADD) applications include granules of 2 granulated water ratios such as BRITESIL® H20 from PQ Corp., and the common source BRITESIL® H24 although liquid grades of various silicates can be used when the composition of ADD has liquid form. Within safe limits, the sodium metasilicate or sodium hydroxide alone or in combination with other silicates can be used in an ADD context to increase the pH of the wash to a desired level.
Bleaching agents Bleaching agents and whitening activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing an agent and one or more bleach activators. Bleaching agents are typically at levels of from about 1% to about 30%, most preferably about 5% to about 20% of the detergent composition, especially for fabric washing. If present, the amount of bleach activators typically about 0.1% to about 60%, most typically about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning or other cleaning purposes now known or known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono and tetrahydrate) may be used herein. Also suitable are organic or inorganic peracids. The organic or inorganic peracids suitable for use in the present invention include: percarboxylic acids and salts; percarbonic acids and salts; perimidic acids and salts; peroxymonosulfuric acids and salts; persulfates such as monopersulfate; peroxyacids such as diperoxydecanedioic acid (DPDA); magnesium perphthalic acid; Perlauric acid; acid tH .Í? rt? l? ít? l? phthaloilamidoperoxycaproic acid (PAP); perbenzoic and alkylperbenzoic acids; and mixtures thereof. A class of suitable organic peroxycarboxylic acids have the general formula: r-R- o: - O- OH wherein R is a substituted alkylene or alkylene group containing 1 to about 22 carbon atoms or a substituted phenylene or phenylene group, and Y is hydrogen, halogen, alkyl, aryl, -C (0) OH or -C (0) ) OOH. Organic peroxyacids suitable for use in the present invention may contain either one or two peroxy groups and may be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted acid has the general formula: wherein Y may be, for example, H, CH 3, CH 2 Cl, C (0) OH, or C (0) OOH; and n is an integer from 1 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted acid has the general formula: where Y can be, for example, hydrogen, alkyl, haloalkyl, halogen, C (0) OH or C (O) OOH.
Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as: (i) peroxybenzoic acid and peroxybenzoic acid substituted with ring, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium hexahydrated salt), and acid o-carboxybenzamidoperoxyhexanoic (sodium salt); (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, for example, peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-octylsuccinoyl) amino-peroxycaproic acid (SAPA) and N, N acid -phthaloylaminoperoxycaproic (PAP); (iii) amidoperoxyacids, for example mononilamide either peroxysuccinic acid (NAPSA) or peroxyadipic acid (NAPAA). Typical diperoxy acids useful in the present invention include alkyl diperoxy acids and aryl diperoxy acids, such as: (iv) 1,2-diperoxydodecanedioic acid; (v) 1,9-diperoxyazelaic acid; (vi) diperoxy fibersic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyliperoxybutane-1,4-dioic acid; (viii) 4,4'-sulfonylbisperoxybenzoic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781; Hartman, issued November 20, 1984, patent of E.U.A. 4,634,551 to Burns et al., European patent application 0, 133,354, Banks et al., Published February 20, 1985 and patent of E.U.A. 4,412,934, Chung et al. issued November 1, 1983. The sources also include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. 4,634,551, issued on January 6, 1987 to Burns et al. Persulfate compounds such as for example OXONE, commercially manufactured by E.l. DuPont de Nemours of Wilmington, DE, may also be employed as a suitable source of peroxymonosulfuric acid. Particularly preferred peracid compounds are those having the formula: or wherein R is C 1-4 alkyl and n is integer from 1 to 5. a particularly preferred peracid has the formula wherein R is CH 2 and n is 5, ie, phthaloylaminoperoxycaproic acid (PAP) as described in U.S. Patents. Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431. PAP is available from Ausimont SpA under the trade name of Euroco. The peracids used in the present invention preferably have a solubility in aqueous liquid compositions measured at 20 ° C from about 10 ppm to about 1500 ppm, most preferably from 50 ppm to about 1000 ppm, most preferably still from about 50 ppm to about 800 ppm. Solubility is measured at 20 ° C. In a particularly preferred embodiment of the present invention, the peracid has an average particle size of less than 100 microns, most preferably less than 80 microns, most preferably still less than 60 microns. Most preferably, when the peracid is PAP, it has an average particle size of between about 20 and about 50 microns. Alternatively, although not preferred, the bleach may be a chlorine bleach. The chlorine bleaches can be any convenient conventional chlorine bleaches. Such compounds are often divided into two categories, namely inorganic chlorine bleach and organic chlorine bleach. Examples of the former are hypochlorites such as sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite. Another example of an inorganic chlorine bleach useful in the present invention is chlorinated trisodium phosphate dodecahydrate: Examples of the latter are isocyanurates, such as potassium dichloroisocyanurate, sodium dichloroisocyanurate. Examples of other organic chlorine bleaches useful in the present invention are 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, dicoramine T, N, N'-dichlorobenzoylenurea, paratoluensulfon-dichloroamide, trichloromethylamine, N-chloroamelin, N-chlorosuccinimide, N, N'-dichloroazodicarbonamide, N-chloroacetylurea, N, N'-dichlorobiuret and chlorinated dicyandamide. Preferably, the chlorine bleach is inorganic chlorine bleach, most preferably it is sodium hypochlorite. Another category of bleaching agent that can be used without restriction comprises percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and hyperoxydedecandioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, Hartman, issued November 20, 1984, the 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, US Patent. 4,412,934 Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the U.S. Patent. 4,634,551 issued on January 6, 1987 to Burns et al. Peroxygen bleaching agents can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. l.
Persulfate bleach (e.g., OXONE, commercially manufactured by DuPont) can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles being less than about 200 microns and not more than 10% of said particles being larger than approximately 1, 250 microns. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial supplies such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, perborates, percarbonates, etc., are preferably combined with bleach activators, which lead to in situ production in the aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the activator of bleach. Various non-limiting examples of activators are described in the U.S. Patent. 4,9151, 854 issued April 10, 1990 to Mao et al., And in the U.S. Patent. 4,412,934. Typical nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylamine (TAED) activators and mixtures thereof can also be used. See also E.U.A. 4,634,551 for other typical bleaches and activators useful herein.
Blanket activators Bleach activators useful herein include amides, imides, esters and anhydrides. Commonly at least one substituted or unsubstituted acyl portion is present, covalently connected to a residual group as in structure R-C (0) -L. In a preferred mode of use, the bleach activators are combined with a source of hydrogen peroxide, such as perborates or percarbonates in a single product. Conveniently, the individual product leads to in situ production in aqueous solution (ie, during the washing process) of the perca rboxylic acid corresponding to the bleach activator. The product itself can be hydrous, for example a powder, provided that the water is controlled in an amount and mobility such that storage stability is acceptable. Alternatively, the product may be an anhydrous solid or liquid. In another mode, the bleach or oxygen bleach activator is incorporated in a pretreatment product, such as a stain removal bar; previously treated, soiled substrates can be exposed to such treatments, for example from a peroxygen source. With respect to the bleach activator structure RC (0) L, the atom in the residual group connecting to the peracid-forming acyl portion R (C) 0- is very typically O or N. The bleach activators may be Peracid formers not loaded, positively or negatively charged and / or residual groups not loaded, positively or negatively charged. One or more peracid forming portions or . ****. '% * residual groups may be present. See, for example, E.U.A. 5,595,967, E.U.A. 5,561, 235, E.U.A. 5,560,862 or the bis- (peroxycarbonic) system of E.U.A. 5,534,179. Mixtures of suitable bleach activators can also be used. The bleach activators may be substituted with electron donating or electron releasing moieties either in the residual group or in the peracid forming portion or portions, changing their reactivity and making them more or less suitable for particular pH or washing conditions. For example, electron acceptor groups such as N02 improve the effectiveness of bleach activators intended for use under mild pH washing conditions (eg, from about 7.5 to about 9.5). An extensive and exhaustive description of suitable bleach activators and suitable residual groups, and how to determine suitable activators, can be found in the patents of E.U.A. 5,686,014 and 5,622,646. Cationic bleach activators include the types of quaternary carbamate, quaternary carbonate, quaternary ester and quaternary amide, providing a range of peroxyimidic, peroxycarbonic or cationic peroxycarboxylic acids to the wash. An analogous but non-cationic palette of bleach activators is available when quaternary derivatives are not desired. In more detail, the cationic activators include activators substituted with quaternary ammonium of WO 96-06915, E.U.A. 4.7151, 015 and 4,397,757, EP-A-284292, EP-A-331, 229 and EP-A-03520. Also useful are cationic nitriles as described in EP-A-303,520 and in the European patent specification 458,396 and 464,880. Other types of nitrile have electron acceptor substituents as described in E.U.A. 5,591, 378. Other descriptions of bleach activators include GB 836,988; 864,798; 907,356; 1, 003,310 and 1, 519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; US patents Nos. 1, 246,339, 3,332,882; 4,128,494; 4,412,934 and 4,675,393, and the phenol ester sulfonate of alkanoyl amino acids described in E.U.A. 5,523,434. Suitable bleach activators include any type of acetylated diamine, either hydrophilic or hydrophobic in character. One of the above classes of bleach precursors, preferred classes include esters, including acyl phenols sulfonates, acylalkyl phenols sulfonates or acyloxybenzenesulfonates (residual group OBS); the acylamides; and the peroxyacid precursors substituted with quaternary ammonium including the cationic nitriles. Preferred bleach activators include N.N.N'N'-tetraacetyl ethylenediamine (TAED) or any of its close relatives including the triacetyl derivatives or other non-symmetrical derivatives. TAED and acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach activators. Depending on the application, acetyltriethyl citrate, a liquid, also has some utility, as does phenylbenzoate.
Preferred hydrophobic bleach activators include sodium nonanoyloxybenzenesulfonate (NOBS or SNOBS), N- (alkanoyl) aminoalkanoyloxybenzenesulfonates, such as 4- [N-8nonanoyl) aminohexanoyloxy] -benzenesulfonate or (NACA-OBS) as described in the US Pat. USA 5,534,642 and in EPA 0 355 384 A1, types of substituted amide described in detail below, such as NAPAA-related activators, and activators related to certain imidoperacid bleach, for example as described in the US patent. 5,061, 807, issued on October 29, 1991 and assigned to Hoechst Aktiengesellschaft in Frankfurt, Germany and the patent application open to the Japanese public (Kokai) No. 4-28799. Another group of peracids and bleach activators of the present invention are those derivable from acyclic imidoperoxycarboxylic acids and salts thereof. See patent of E.U.A. 5415796, and cyclic imidoperoxycarboxylic acids and salts thereof, see patent E.U.A. 5,061, 807, 5,132,431, 5,654.2629, 5,246,620, 5,419,864 and 5,438,147. Other suitable bleach activators include sodium 4-benzoyloxybenzenesulfonate (SBOBS); Sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; Sodium 4-methyl-3-benzoyloxybenzoate (SPCC); trimethylammonium toluyloxybenzenesulfonate; or sodium 3,5,5-trimethyl hexanoyloxybenzenesulfonate (STHOBS). Bleach activators can be used in an amount of up to 20%; preferably 0.1-10% by weight of the composition, although st? -? Re J.jfctj »m,? .Xf.1 ... V X.» Í.? higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or forms intended for automated dosing in the washing apparatus. Highly preferred bleach activators useful herein are substituted with amine and an extensive and exhaustive description of these activators can be found in U.S. Pat. 5,686,014 and 5,622,646. Other useful activators described in E.U.A. 4,966,723 are of the benzoxazine type, such as a CeH 4 ring to which it is fused in the 1,2-position-a -C (0) OC (R 1) = N- moiety. A highly preferred activator of the benzoxazine type is: Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having a pH of about 6 to about 13, preferably about 9.0 to about 10.5, during use. Typically, for example, activators with electron-withdrawing portions are used for pH ranges close to neutral or sub-neutral. The alkalis and pH regulating agents can be used to ensure that pH. Acyl lactam activators are very useful in the present invention, especially the acylcaprolactams (see for example WO 1: 94.28102 A) and acylvalerolactams (see E.U.A. 5,503,639). See also E.U.A. 4,545,784 which describes acylcaprolactams including benzoyl caprolactam adsorbed on sodium perborate. In certain preferred embodiments of the invention, NOBS, lactam activators, imide activators or functional amide activators, especially the more hydrophobic derivatives, are desirably combined with hydrophilic activators such as TAED, typically at weight ratios of hydrophobic activators: TAED in the range from 1: 5 to 5: 1, preferably from about 1: 1. Other suitable lactam activators are alpha-modified, see WO 96-22350 A1, July 25, 1996. Lactam activators, especially the more hydrophobic types, are desirably used in combination TAED, typically at weight ratios of amino derivatives or Caprolactam activators: TAED in the range of 1: 5 to 5: 1, preferably of about 1: 1. See also bleach activators having a residual group of cyclic amidine described in E.U.A. 5,552,556. Non-limiting examples of additional activators useful in the present invention are found in E.U.A. 4,915,854, E.U.A. 4,412,934 and 4,634,551. The hydrophobic activator nonanoyloxybenzenesulfonate (NOBS) and the hydrophilic activator tetraacetylethylenediamine (TAED) are typical and mixtures thereof can also be used. Additional activators useful herein include those of E.U.A. 5,545,349, which is also incorporated herein by reference. i? ~ Bleaches other than oxygen whitening agents are also known in the art and can be used here. One type of non-oxygen whitening agent of particular interest includes photoactivated whiteners such as sulfonated zinc and / or aluminum phthalocyanines. See patent of E.U.A. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, the detergent compositions will typically contain from about 0.025% to about 1.25% by weight, of said bleaches, especially sulfonated zinc phthalocyanine.
Bleach catalysts The compositions of the present invention and the methods of the present invention can utilize metal-containing bleach catalysts that are effective for use in ADD compositions. Bleach catalysts containing manganese and cobalt are preferred. For examples of suitable catalysts, see U.S. Patents. Nos. 4, 246,612, 5,804,542, 5,798,326, 5,246,621, 4,430,243, 5,244,594, 5,597,936, 5,705,464, 4,810,410, 4,601, 845, 5,194,416, 5,703,030, 4,728,455, 4,711, 748, 4,626,373. 4,119,557, 5,114,606, 5,599,781, 5,703,034, 5,114,611, 4,430,243, 4,728,455 and 5,227,084; European Patent Nos. 408,131, 549,271, 384m503, 549,272, 224,952 and 306,089; German Patent No. 2,054,019; Canadian Patent No. 866,191. Cobalt catalysts (III) having the formula are preferred: CoKNHaJníM'JmlB'bT'tQqPp] Yy where cobalt is in the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; very 5 preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counterions present in a number y, where y is an integer of 1 to 3 10 (preferably 2 to 3, most preferably 2 when Y is an anion with charge -1), to obtain a balanced salt as to charge, Y preferred is selected from the group consisting of chloride, iodide, I3", formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF4", B (Ph) 4", phosphate, phosphite, silicate, tosylate, methanesulfonate and combinations of 15 themselves [optionally, Y can be protonated if there is more than one anionic group in Y, for example HPO-42", HCO3-, H2PO4-, etc., and in addition, Y can be selected from the group consisting of non-inorganic anions. traditional such as anionic surfactants (eg, linear alkylbenzene sulphonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and / or anionic polymers (eg, polyacrylates, polymethacrylates, etc.); At least one of the coordination sites linked to cobalt is labile under conditions of automatic dishwashing use and the remaining coordination sites stabilize the Cobalt hydrolysis under automatic dishwashing conditions such as the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode. Cobalt catalysts are preferred having the formula: [C? (NH 3) n (M,) m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); M 'is a labile coordinating portion, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 10 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferably 1); m + n = 6; and Y is an appropriately selected counter ion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is an anion charged with -1), to obtain a balanced salt in charge . The preferred cobalt catalyst of this type useful herein are the cobalt-pentamine chloride salts having the formula [Co (NH3) 5CI] Yy and especially [Co (NH3) 5CI] CI2. Very preferred are the compositions of the present invention which use cobalt bleach catalysts (III) having the 20 formula: [Co (NH3) p (M) m (B)] Ty where the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more appropriately selected counterions present in number y, where y is an integer to obtain a salt balanced in charge (preferably y is 1 to 3, most preferably 2 when T is an anion charged with -1); and wherein said catalyst has a base hydrolysis constant of less than 0.23 M-1 s (25 ° C). The most preferred cobalt catalyst useful herein are salts of cobalt pentaminoacetate having the formula [Co (NH3) 5OAc] Ty, wherein OAc represents an acetate portion and especially cobalt pentaminoacetate chloride, Co (NH3) 5OAc] Cl2; as well as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5? Ac] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2. As a practical matter, and not by way of limitation, the cleaning compositions and cleaning methods herein can be adjusted to provide the order of at least one part per one hundred million of the active bleach catalyst species in the medium of aqueous washing, and preferably will provide from about 0.01 ppm to about 25 ppm, most preferably from about 0.05 ppm to about 10 ppm, and most preferably still from about 0 ppm to about 5 ppm, of the bleach catalyst species in the washing solution. In order to obtain such levels in the automatic dishwashing compositions of the present invention will comprise from about 0.0005% to about 0.2%, most preferably from about 0.004% to about 0.08% of the bleach catalyst of the cleaning compositions.
Detergency builders Builders can operate through a variety of mechanisms including the formation of soluble or insoluble complexes with hardness values, by ion exchange, and by providing a more favorable surface for the precipitation of hardness ions than the surfaces of items that are going to be cleaned. The level of the builder may vary depending on the final use of the composition and the physical form of the composition. For example, formulations with high surfactant content can be without detergency improvement. The level of the builder may vary depending on the final use of the composition and its desired physical form. The compositions will comprise at least about 0.1%, preferably from about 1% to about 90%, most preferably from about 5% to about 80%, most preferably still from about 10% to about 40%, by weight, of the detergency builder However, lower or higher levels of detergency builder are not excluded.
* ^^^ "A tofe-a fc * ei The builders suitable herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts, carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than carbonate or sodium sesquicarbonate; organic mono-, di- and tetracarboxylates, especially the carboxylates which are not water-soluble surfactants and in the form of acid, sodium, potassium or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including the types aliphatic and aromatic; and phytic acid. These may be supplemented with borates, for example, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other fillers or vehicles that may be important for the design of stable detergent compositions containing surfactants and / or builders. of detergency. Mixtures of builders can be used, sometimes called "builders systems", and typically comprise two or more conventional detergency builders, optionally supplemented with chelators, pH regulators or fillers, although the latter materials are taken into account separately when describing the amounts of builders. materials in the present. In terms of relative amounts of surfactant and builder in the present detergents, preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60: 1 to about 1: 80 Certain detergents that are preferred have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, preferably 0.95: 1 to 3.0: 1.0. Phosphate-containing builders are commonly preferred when allowed by law, and include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, exemplified by tripolyphosphates, pyrophosphates, vitreous polymeric meta-phosphates and phosphonates. Where phosphorus-based builders can be used, the various alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate well known can be used. Phosphonate builders such as eta n-1-hydroxy-1,1-diphosphonate and other known phosphonates (see for example U.S. Patent 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) may also be used although said materials are more commonly used in a low level mode as chelators or stabilizers. Phosphate builders for use in granular compositions are well known. These include, but are not limited to, alkali metal, ammonium and alkanol ammonium salts of polyphosphonates (exemplified by the glassy polymeric tripolyphosphates, pyrophosphates and metaphosphates). The sources of phosphate builder are described in detail in Kirk Othmer, 3rd edition, vol. 17, pp. 426-47 and in "Advanced Inorganic Chemistry" by Cotton and Wiikinson, pp. 394-400 (John Wiley and Sons, Inc., 1972). The preferred levels of phosphate builders of the present invention are from about 10% to about 75%, preferably from about 15% to about 50%, of phosphate builder. The phosphate builders optionally can be included in the compositions of the present invention to help control the hardness of minerals. Detergency builders are typically used in automatic dishwashing to aid in the removal of particulate soils. Carbonate builders include alkaline earth metal and alkali metal carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any multiple salts of calcium carbonate such as those that have the composition 2Na2C? 3.CaC? 3 when they are anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially the forms that have high surface areas in relation to compact calcite can be very useful, for example as seeds. Various grades and types of sodium carbonate and sodium sesquicarbonate can be used, some of which are i &A? i? ± it * ... ¿.. ^ .. í: - ,. # particularly useful as vehicles for other ingredients, especially detersive surfactants. Suitable organic builders include polycarboxylate compounds, including dicarboxylates and tricarboxylates that are non-surfactant and water soluble. Very typically, the builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When they are in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, E.U. 3,128,287, April 7, 1964, and Lamberti et al., E.U. 3,635,830, January 18, 1972. See also builders of "TMS / TDS" of E.U. 4,663,071, Bush et al., May 5, 1987; and other ether polycarboxylates including cyclic and alicyclic compounds, such as those described in the U.S.A. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include eterhydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as melific acid, succinic acid, acid polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. The citrates, for example, citric acid and soluble salts thereof, are important carboxylate builders because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicates. The citrates can also be used in combination with zeolite, the types of BRIRESIL mentioned below, and / or layered silicate builders. The Oxydisuccinates are also useful in said compositions and combinations. Oxydisuccinates are also especially useful in said compositions and combinations. When allowed, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and orthophosphate may be used. 15 of sodium. Phosphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used, for example, those of US Pat. No. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 and may have desirable antifouling properties. Certain detersive surfactants or their counterparts of 20 short chain also have detergency builder action. For unambiguous formula reasons, when they have surfactant capacity, these materials are taken into account as detersive surfactants. The preferred types of builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in E.U.A. 4,566,984, Bush, January 28, 1986. Succinic acid builders include alkylsuccinic and alkenyl succinic acids of C5-C20 and salts thereof. Succinate builders include: lauryl succinate, myristiisuccinate, palmitiisuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated into the compositions as surfactant / enhancer materials of detergency alone or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide additional detergency builder activity but are generally not desired. Such use of fatty acids will generally result in a decrease in foaming in laundry compositions. Fatty acids or their salts are undesirable in automatic dishwashing (ADD) modalities in situations where soap creams can be formed and deposited on the dishes. Other suitable polycarboxylates are described in E.U.A. 4,144,226, Crutchfield et al., March 13, 1979 and in US Pat. No. 3,308,067, Diehl, March 7, 1967. See also Diehl, E.U.A. 3,723,322. Other types of inorganic builders materials that can be used have the formula (M?) Cay (C03) z where x and i ? ? A t * ¿? are integers from 1 to 15, and is an integer from 1 to 10, z is an integer from 2 to 25, M, are cations, at least one of which is soluble in water, and the equation?, = 1- 15 (x, multiplied by the valence of M,) + 2y = 2z is satisfied in such a way that the formula has a neutral or "balanced" charge. These builders are called "mineral builders" here. Hydration waters or anions other than carbonate can be added, as long as the total charge is balanced or neutral. The charge or valence effects of said anions must be added to the correct side of the previous equation. Preferably, a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, most preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, is present. thereof. Non-limiting examples of non-carbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate, and mixtures thereof. Preferred builders of this type that are preferred in their simplest forms are selected from the group consisting of Na 2 Ca (C 0 3) 2, K 2 Ca (C 0 3) 2, Na 2 Ca 2 (C 0 3) 3, NaK Ca (C03) 2, NaK Ca 2 (C03) 3, K2Ca2 (C03) 3 and combinations thereof. An especially preferred material for the detergency builder described herein is Na2Ca (C03) 2 in any of its crystalline modifications. Suitable detergency builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any or combinations of the following minerals: afghanite, andersonite, ashcroftinaY, beyerita, borcarita, burbankite, butschliita, cancrinite, carbocemaita, carletonita , davina, donnaiitaY, fairchildita, ferrisurita, franzinita, gaudefroyita, gaylussita, girvasita, gregorita, jouravskita, kampahaugita And, kettnerita, khanneshita, lepersonitaGd, lyotita, mckelveyitaY, microsomita, mroseita, natrofairchildita, nierereita, remonditaCe, sacrofanita, schrockingerita, shortita, surita, tunisita, tuscanita, tirolita, vishnevita and zemkorita. Preferred mineral forms include Niererite, fairchildite and shortita. The detergency builders are selected from aluminosilicates and silicates, for example to help control mineral hardness, especially Ca and / or Mg in the wash water, or to assist in the removal of particulate soils from the surfaces. Suitable silicate builders include the water-soluble and water-soluble types, and include those having a chain, layer or three-dimensional structure, as well as the amorphous-solid or unstructured-liquid types. Alkali metal silicates are preferred, particularly those liquids and solids having a Si 2: Na 2+ ratio. in the range from 1.6: 1 to 3.2: 1, including, particularly for the purpose of automatic dishwashing, 2-ratio solid aqueous silicates marketed by PQ Corp. under the brand BRITESIL®, eg, BRITESIL H20; and layered silicates, for example those described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is silicate ..... t,? morphology d-Na2SiOs crystalline and aluminum free stratified sold by Hoechst, and is especially preferred in granular laundry compositions. See preparation methods in German Application DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSiX? 2? +? And H20 where 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. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha silicate forms, beta and gamma. Other silicates can also be used such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for bleaches, and as a component of foam control systems. Also suitable for use herein are the crystalline ion exchange materials synthesized or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM20.yS02.zM'0 in where M is Na and / or K, M * is Ca and / or Mg; y / x is 0.5 to 2.0 and z / x is 0.005 to 1.0 as taught in E.U.A. 5,427,711, Sakaguchi et al., June 27, 1995. Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated into pastes or gels. Suitable for the present purposes are those that have the empirical formula: [Mz (AI02) z (Si? 2) and] .xH2 ?, where z and v are integers of at least 6, the molar ratio of zav is in the scale from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, occurring naturally or synthetically derived. An aluminosilicate production method is described in E.U.A. 3,985,669, Krummel et al., October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, as far as is different from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, can be used. Zeolite A has the formula: Na? 2 [(AI02) i2 (Si? 2) i2]. H2? wherein x is from about 20 to about 30, especially about 27. Dehydrated zeolites can also be used (x = 0-10). Preferably, the aluminosilicate has a particle size of 0J-10 microns in diameter. Detergency builders other than silicates can be used in the compositions herein to help control the hardness of the minerals. They can be used together with or instead of aluminosilicates and silicates. Inorganic as well as organic builders can be used. Detergency builders are used in automatic dishwashing to aid in the removal of particulate soils. Inorganic or non-phosphate builders include, but are not limited to, phosphonates, phytic acid; carbonates .to. a ^ 1 (including bicarbonates and sesquicarbonates), sulfates, citrate; zeolite and aluminosilicates. Aluminosilicate builders can be used in the present compositions although they are not preferred for automatic dishwashing detergents (see U.S. Patent 4,605,509 for examples of preferred aluminosilicates). Aluminosilicate builders are of great importance in most heavy duty granular detergent compositions currently marketed, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula Na2? Al203 xSiOz and H20 where z and y integers of at least 6, the molar ratio of zay is on the scale of 1.0 to about 0.5 and x is an integer of about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available available. These aluminosilicates can be crystalline or amorphous in nature and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in the U.S.A. 3,985,669, Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite P (B), Zeolite X.
Li In another embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2 [(AI02)? 2 (SiO2)? 2] xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of 0J-10 microns in diameter. The individual particles may conveniently be even smaller than microns to further assist the exchange kinetics by maximizing the surface area. The high surface area also increases the usefulness of aluminosilicates as adsorbents for surfactants, especially in granular compositions. Aggregates of aluminosilicate silicate particles may be useful, a single aggregate having dimensions adjusted to minimize segregation in granular compositions, while the aggregate particle remains dispersible to individual submicron particles during washing. As with other detergency builders such as carbonates, it may be convenient to use zeolites in any physical or morphological form adapted to promote the function of the surfactant vehicle, and the appropriate particle sizes can be freely selected by the formulator. t Á m *. The polymeric soil release agent The compositions according to the present invention may optionally comprise one or more soil release agents. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon and hydrophobic segments, to deposit on hydrophobic fibers and remain adhered to them upon completion of the washing cycle and This way serve as an anchor for the hydrophilic segments. This may allow stains that occur after treatment with the soil release agent to be more easily cleaned in subsequent washing procedures. If used, the soil release agents will generally comprise from about 0.01% to about 10%, preferably from about 0.1% to about 5%, most preferably from about 0.2% to about 3% by weight of the composition. The following, all included by reference, disclose suitable soil release polymers for use in the present invention. E.U.A. 5,691, 298 Gosselink et al., Issued November 25, 1997; E.U.A. 5,599,782 Pan et al., Issued February 4, 1997; E.U.A. 5,415,807 Gosselink et al., Issued May 16, 1995; E.U.A. 5,182,043 Morrall et al., Issued January 26, 1993; E.U.A. 4,956,447 Gosselink et al., Issued September 11, 1990; E.U.A. 4,976,879 Maldonado et al., & A k issued on December 11, 1990; E.U.A. 4,968,451 Scheibel et al., Issued November 6, 1990; E.U.A. 4,925,577 Borcher, Sr. et al., Issued May 15, 1990; E.U.A. 4,861, 512 Gosselink, issued August 29, 1989; E.U.A. 4,877,896 Maldonado et al., Issued October 31, 1989; E.U.A. 4,702,857 Gosselink et al., Issued October 27, 1987; E.U.A. 4,711, 730 Gosselink et al., Issued December 8, 1987; E.U.A. 4,721, 580 Gosselink issued on January 26, 1988; E.U.A. 4,000,093 Nicol et al., Issued December 28, 1976; E.U.A. 3,959,230 Hayes, issued May 25, 1976; E.U.A. 3,893,929 Basadur, issued July 8, 1975; and European patent application 0 219 048, published April 22, 1987 by Kud et al. Suitable soil release agents are described in E.U.A. 4,201, 824 Voilland et al .; E.U.A. 4,240,918 Lagasse et al .; E.U.A. 4,525,524 Tung et al .; E.U.A. 4,579,681 Ruppert et al .; E.U.A. 4,220,918; E.U.A. 4,787,989; EP 279,134 A, 1988 by Rhone-Poulenc CHEMIE; EP 457,205 A of BASF (1991); and DE 2,335,044 from Unilever N.V., 1974; all incorporated here by reference.
Clay dirt remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The granular detergent compositions containing these compounds i h. 4 typically comprise from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain from about 0.01% to about 5%.
Polymeric dispersion agents Polymeric dispersion agents can be advantageously used at levels of from about 0.1% to about 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 may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the overall detergency builder, when used in combination with other builders (including lower molecular weight polycarboxylates) by growth inhibition. of crystals, peptization of release of dirt into particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid. The presence of the polymeric polycarboxylates in the present or polymeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been presented, for example, in Diehl, patent of E.U.A. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid 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 said copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably about 5,000 to 75,000 and very - - * - - "- - - ^^ - - ^ * - ^ ~ -m ~ ^ -L- * > ~ *? > -l? -? * Preferably around 7,000 to 65,000. the acrylate segments relative to the maleate segments in said copolymers generally range from about 30: 1 to about 1: 1, most preferably about 10: 1 to 2: 1. The water soluble salts of said acrylic acid copolymers / Maleic acid may include, for example, the alkali metal, ammonium and substituted ammonium salts The soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published on December 15. of 1982, as well as in EP 193,360, published on September 3, 1986, which also discloses polymers comprising hydroxypropylacrylate Other useful dispersing agents include the terpolymers of maleic / acrylic / vinyl alcohol.These materials are also described in EP 193,360 , including, for example, the 45/45/10 maleic / acrylic / vinyl alcohol polymer. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes vary from about 500 to about 100,000, preferably from about 1,000 to about 50,000 and most preferably from about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of - .-.-VJ. J. j. A i. The polyaspartate preferably has a molecular weight (average) of about 10,000.
Brightener Any optical brighteners or other brightener or whitening agents known in the art can be incorporated at levels typically from about 0.01% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups that include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanin, 5,5-dibenzotifen dioxide, azole derivatives , 5- and 6-membered ring heterocycles, and various other agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S. patent. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the Verana PHORWHITE series of brighteners. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4, -bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins.
.. -. ". '» A »tj. I: Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton.
Dye transfer inhibiting agents The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, phthalocyanine of manganese, peroxidases and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. Very specifically, the preferred polyamine N-oxide polymers for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (0) 0-, -S-, -O-, -N =; x is 0 or 1; Y . **, *. ^, m- * w. * -fcsfci ^ R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. The preferred N-oxides of polyamine are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: wherein Ri, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or forms part of any of the 15 groups mentioned above. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has 20 dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in eleven where one type of monomer is an N-oxide amine and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, 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. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more 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 the poly-4-vinylpyridine N-oxide having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4 Polymer copolymers of N-vinylporrolidone and N-vinylimidazole (known as "PVPVl") are also preferred for use herein. Preferably, the PVPVl has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and others, Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are hereby listed by reference). PVPVl copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, 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. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 5,000 to about 50,000. . The PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners.
- The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4.4,, bis [(4-anilino-6- (N-2)] bis-hydroxyethyl) -s-triazin-2-yl) amino] -2 > 2'-stybenedisulfonic and disodium salt. This particular brightener species is commercially sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the compositions herein. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of acid 4,4, -bis [(4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula R is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin- 2-yl) amino] 2,2, -stilbenedisulfonic acid. This particular brightener species is sold commercially under the Tinopal AMS-GX brand by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provides especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVl) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significant dye transfer inhibition. better in aqueous washing solutions than either of those two components of detergent composition when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener compounds may optionally be present in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations.
Foam suppressants Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foam may be of particular importance in so-called "high concentration cleaning processes" such as those described in E.U.A. 4,489,455 and 4,489,574, and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Wiley &; Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto. See the patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as a suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium, as well as ammonium and alkanolammonium salts. The detergent compositions herein may also contain suds suppressants which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, finger aliphatic ketones (eg, stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminoclorotriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. , propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal (eg, K, Na and Li) phosphates and ester phosphates monostearyl. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a boiling point of not less than 100 ° C (atmospheric pressure). The suo of wax hydrocarbons is also known, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressants for detergent compositions. The hydrocarbon foam suppressors are described, i * t ír & TO ?. hM ^ »- - fcJ I '*. - .. -. »» - ... . . . - - ... -, .. ...... - .rL. ^ R.! ... ... JLr. ** ... I ..... A ... ¡LÁRÁ. ? .Íi, 1 example, in the patent of E.U.A No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors that are not surfactants comprise silicone foam 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 chemoabsorbed or fused to the silica. Silicone foam suppressors are well known in the art and are described, for example, in the US patent. 4,265,779, issued May 5, 1981 to Gandolfo et al. And in European patent application No. 89307851.9, published on February 7, 1990 by Starch, M.S. Other silicone foam suppressors are described in U.S. Patent 3,455,839, which relates to compositions and processes for the removal of foam from aqueous solutions by incorporating thereto small amounts of polydimethylsiloxane fluids. i? i ... i i - to - ar - - - * - - * ....... -? r & .A.íí. Mixtures of silicone and silica silanada are described, for example, in the German patent application DOS 2,124,526. Silicone foam removers and foam control agents in granular detergent compositions are described in US Patent 3,933,672, Bartolotta et al., And in US Patent 4,652,392, Baginski et al., Issued March 24, 1987. A Illustrative silicone-based foam suppressant for use herein is a foam suppressing amount of a foam controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1, 500 cs. at 25 ° C; (ii) about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH 3) 3 SiO < | / 2 units of SÍO2 in a unit ratio of (CH3) 3S¡0 < | / 2 to S1O2 units of about 0.6: 1 to about 1.2: 1; and (iii) about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone foam suppressant used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and preferably non-linear.
, Av. To further illustrate this point, typical laundry detergent compositions with optionally controlled foaming will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight percent of said silicone foam suppressant, comprising (1) a non-aqueous emulsion of a primary foam anti-shaving 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 for promoting the reaction of blend components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without polypropylene glycol. See also patents of E.U.A. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994, and US patents. 4,639,489 and 4,749,740, Aizawa et al. In column 1, row 46 to column 4, row 35. The silicone foam suppressant of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a lower average molecular weight of about 1, 000, preferably between about 100 and 800. The copolymers of .i. * j, polyethylene glycol and polyethylene / polypropylene of the present have a solubility in water at room temperature other than about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, most preferably between about 100 and 800, most preferably still between 200 and 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300. A weight ratio of between about 1: 1 and 1: 10, most preferably between 1: 3 and 1: 6, of polyethylene glycol polyethylene-polypropylene glycol copolymer is preferred. Preferred silicone foam suppressors and used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably, they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressors useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in US Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include alkyl alcohols of CQ-C < Q having a chain of Ci-C-iß- A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the tradename ISALCHEM 123 from Enichem. The suppressors of ,. -foA ,. «i., 1 Mixed foam typically comprises mixtures of alcohol + silicone at a weight ratio of 1: 5 to 5: 1. For any detergent compositions that are to be used in automatic washing machines, the foam should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foam to result in a low foaming laundry detergent for use in automatic washing machines. The compositions herein will generally comprise from 0% to about 10% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts thereof, will typically be present in amounts up to about 5%, by weight, of the detergent composition. Preferably, about 0.5% to about 3% of fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts of up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower quantities to effectively control foaming. Preferably from about 0.01% to about 1% silicone foam suppressant is used, most preferably from about 0.25% to about 0.5%. As used herein, these values in percent by weight include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from about 0.01% to about 2% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.
Alkoxylated polycarboxylates Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional fat removal performance. Said materials are described in WO 91/08281 and PCT 90/01815, p. 4 et seq., Incorporated herein by way of reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chains have the formula - (CH2CH2?) M (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are attached by ester to the "base structure" of the polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. Said alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight of the compositions herein.
Fabric Softeners Various fabric softeners that soften during washing, especially the impalpable smectite clays of the U.S. Patent may optionally be used. 4,062,647, Storm and Nirschi, issued December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% by weight in the compositions herein to provide softening benefits concurrently with the cleaning of fabrics. Clay-based softeners may be used in combination with amine and cationic softeners as described, for example, in the U.S. patent. 4,375,416, Crisp et al., March 1, 1983 and in the patent of E.U.A. 4,291, 071, Harris et al., Issued September 22, 1981. The compositions of the present invention may be of a physical form, depending on the final use of the composition. Typically, the compositions of the present invention may be in the form of a liquid, liquid-gel, gel, thixotropic gel, powder, granule (such as high bulk density granules or so-called "fluffy" granules), paste, tablet, bar. and similar.
Similarly, the compositions of the present invention can be used in a variety of different applications. Such compositions would include hard surface cleaners, bleaches, automatic dishwashing, LDL's HDL's (both aqueous and non-aqueous) heavy duty laundry compositions, laundry pre-conditioners, fabric softeners, shampoos, personal cleansers and the like. The compositions of the present invention are especially suitable for use in automatic dishwashing, bleaching and HDL compositions. The compositions of the present invention may be in the form of personal cleansing compositions or shampoos. Typically these compositions contain an auxiliary ingredient of shampoo composition which is preferably selected from antidandruff agents (preferably platelet pyridinothione salt crystals, sulfur, octopirox, selenium sulfide, ketoconazole and pyridinothione salts), surfactant coagents (preferably selected from the agent anionic surfactant, nonionic surfactant, cationic surfactant, amphoteric surfactant, zwitterionic surfactants and mixtures thereof), silicone hair conditioning agent, polyalkylene glycols, suspending agent, water, water soluble cationic polymeric conditioning agents, agents hydrocarbon conditioners, foam enhancers, preservatives, thickeners, co-surfactants, dyes, perfumes, solvents, styling polymers, antistatic agents, deposition polymers, styling and solvent polymers, phase-separated polymers rsa, hydrocarbon conditioning agents, silicone conditioning agents, suspending agent, cationic distribution agents, phase separation initiators and pediculocides and mixtures thereof. These and other materials suitable for incorporation into shampoo compositions can be found in the patent applications of E.U.A. series No. 60/061, 975 filed on October 17, 1997 (case No. 6882P) and 60/061, 916 filed on October 17, 1997 (case No. 6884P). The compositions of the present invention may also be in the form of LDL compositions. These LDL compositions include, in addition to those previously detailed, additives typically used in LDL formulations, such as diamines, divalent ions, foam enhancing polymers, soil release polymers, polymeric dispersants, polysaccharides, abrasives, bactericides, rust inhibitors. , detergency builders, enzymes, dyes, perfumes, thickeners, antioxidants, processing aids, foam enhancers, pH regulators, antifungal or mildew control agents, insect repellents, anticorrosive aids and chelators. The compositions of the present invention may be in the form of a non-aqueous liquid, heavy-duty detergent compositions in the form of a stable suspension of solid particulate material. »3 ^ Substantially insoluble Hfrlj dispersed through a liquid phase containing surfactant, structured. Suitable types of non-aqueous surfactant liquids that can be used to form the liquid phase of the compositions in the present invention include alkoxylated alcohols, block polymers of ethylene oxide (EO) -propylene oxide (PO) polyhydroxy amides of fatty acid, alkylpolysaccharides and the like. The liquid phase of the HDL compositions in the present invention may also comprise one or more non-aqueous organic solvents that do not contain surfactant. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions in the present invention include non-vicinal d-C 1 alkylene glycols, lower alkylene glycol monoalkyl ethers, lower molecular weight polyethylene glycols, methyl esters and molecular weight amides lower and similar. Also contemplated are mixtures of non-aqueous organic solvents that do not contain surfactant and non-aqueous surfactant liquids. The non-aqueous liquid phase of the HDL compositions of this invention is prepared by combining with the non-aqueous organic liquid diluents heretofore described a surfactant which is generally but not necessarily selected to add structure to the nonaqueous liquid phase of the detergent compositions of the present invention. The i .. structuring surfactants can be of the anionic, nonionic, cationic and / or amphoteric types. The most preferred type of anionic surfactant to be used as a structurant in the HDL compositions of the present invention comprises the linear alkylbenzene sulphonate (LAS) surfactants. The non-aqueous HDL compositions of the present invention preferably comprise a solid phase particulate material that is dispersed and suspended within the liquid phase. Generally, said particulate material will vary in size from about OJ to 1500 microns, most preferably from about OJ to 900 microns. Most preferably, said material will vary in size from about 5 to 200 microns. As mentioned above, the surfactants of the present invention can be included in a fabric softening composition. Suitable materials for incorporation into fabric softening compositions in addition to the surfactants of the present invention can be found in the patent applications of E.U.A. series No. 5,830,845, granted on November 3, 1998; 5,929,025, issued July 27, 1999; 5,877,745, issued March 2, 1999; 5,977,055, issued November 2, 1999; 5,845,200, granted on December 29, 1998; and 5,686,376, Rusche et al., issued November 2, 1999. The particulate material used in the present invention may comprise one or more types of detergent composition components that in particulate form are substantially insoluble in the non-aqueous liquid phase of the composition. The types of particulate materials that may be used are peroxygen bleaching agent, organic builder, inorganic alkalinity source (preferably 5 include carbonates, bicarbonates, borates, pyrophosphates, orthophosphates, polyphosphates, phosphonates, silicates and metalalkaline metasilicates), colored specks and mixtures thereof. The present invention also comprises aqueous-based liquid detergent compositions. Liquid detergent compositions Aqueous compositions of the present invention comprise a surfactant system that preferably contains one or more detersive co-surfactants in addition to the above-described branched surfactants. The additional co-surfactants can be selected from the nonionic detersive surfactant, detersive surfactant 15 anionic, detersive surfactant, detersive agent, 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. These surfactants were described 20 above. In addition to the liquid and solid phase components as described above, the aqueous and non-aqueous based detergent compositions can and preferably will contain some other components optional Such optional components may be in liquid or solid form. The optional components can be dissolved in the liquid phase or they can be dispersed within the liquid phase in the form of fine particles or droplets. Suitable optional materials include, for example, chelating agents, enzymes, detergency builders, bleach catalysts, bleach activators, thickeners, viscosity controlling agents and / or dispersing agents, foam enhancers, liquid bleach activators, transfer inhibitors. of dye, solvents, supressors of foam, agent of elasticity of structure, 10 antiredeposition agents, to illustrate only a few possible optional ingredients. Some of the materials that can optionally be used in the compositions of the present invention are described in greater detail. Further details on suitable auxiliary ingredients for HDL compositions, methods of preparation of the The same and use in the compositions can be found in the patent applications of E.U.A. series No. 60 / 062,087 (case No. 6876P) and 60/061, 924 (case No. 6877P).
Other ingredients The detergent compositions preferably will further comprise one or more detersive auxiliaries selected from the following: electrolytes (such as sodium chloride), polysaccharides, abrasives, bactericides, anti-rust inhibitors, dyes, antifungal agents or mold control, insect repellents, perfumes, hydrotropes, thickeners, processing aids, foam enhancers, anticorrosive aids, stabilizers and antioxidants. A wide variety of useful ingredients in detergent compositions can be included in the compositions of the present invention, including other active ingredients, vehicles, hydrotropes, antioxidants, processing aids, dyes or pigments, solvents for liquid formulations, etc. If high foaming is desired, foam enhancers such as C10-C16 alkanolamides can be incorporated into the compositions, typically at levels of 1% to 10%. C10-C14 monoethanolamides and diethanolamides illustrate a typical class of such foam boosters. The use of said foam boosters with high foaming auxiliary surfactants such as the above-mentioned amine, betaine and sultaine oxides is also advantageous. An antioxidant may optionally be added to the detergent composition of the present invention. It can be any conventional antioxidant using in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamate, ascorbate, thiosulfate, monoethanolamine (MEA), diethanolamine, triethanolamine, etc. It is preferred that the antioxidant, when present, be in the composition in an amount of from about 0.001% to about 5% by weight. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash solution, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3% -5% of nonionic ethoxylated alcohol surfactant of C13-15 (EO 7 ). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, 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 detergent compositions. In addition, the compositions may comprise a hydrotrope.
Suitable hydrotropes include sodium, potassium, ammonium or water-soluble substituted ammonium of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, and xylene sulfonic acid.
A. ÉJ &J The manufacture of LDL compositions comprising a non-aqueous vehicle medium can be prepared in accordance with the teachings of the US patents. 4,753,570; 4,767,558, 4,772,4123, 4,88,652; 4,892,673; GB-A-2,158,838; GB-A-2J95.125; GB-A-2, 195,649; USES. 4,988,462; E.U.A. 5,266,233; EP-A-255,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); E.U.A. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (10/6/81), incorporated herein by reference. Said compositions may contain various particulate detersive ingredients stably suspended therein. Said non-aqueous compositions therefore comprise a LIQUID PHASE and optionally but preferably a SOLID PHASE, all described in more detail herein and in the cited references. The LDL compositions of this invention can be used to form aqueous wash solutions for use in manual dishwashing. Generally, an effective amount of said LDL composition is added to water to form said aqueous cleaning or soaking solutions. The aqueous solution thus formed is then contacted with the tableware, tableware and kitchen utensils. An effective amount of the LDL compositions of the present invention. added to water to form aqueous cleaning solutions may comprise sufficient amounts to form about 500 to 20,000 ppm of the composition in aqueous solution. Most preferably from about 800 to 5,000 ppm of the detergent compositions of the present invention will be provided in an aqueous cleaning solution. The average particle size of the components of granular compositions according to the invention should preferably be such that no more than 5% of the particles are greater than 1.7 mm in diameter and no more than 5% of the particles are less than 0J. 5 mm in diameter. The average particle size as defined herein is calculated by sifting a sample of the composition in a number of fractions (typically 5 fractions) over a series of Tyler sieves. The fractions by weight thus obtained are plotted against the opening size of the sieves. The average particle size is taken to be the aperture size through which 50% by weight of the sample would pass. The granular laundry compositions according to the present invention typically have a bulk density of 100 g / liter to 1400 g / liter, most preferably 300 g / liter to 1200 g / liter, most preferably still g / liter to 1000 g. /liter.
High Density Detergent Composition Process Various media and equipment are available to prepare high density, high solubility, free-flowing granular detergent compositions (ie, greater than about 550, preferably greater than 650 grams / liter or "g / l. ") according to the present invention.
. .... "Rkr? .Jt ri.Jßri 14 Current commercial practice in the field employs spray-drying towers for making granular laundry detergents which often have a density of less than about 500 g / l. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passing through a spray-drying tower, using conventional techniques, at temperatures from about 175 ° C to about 225 ° C. However, if spray drying is used as part of the overall process of the present invention, additional or alternative process steps as described herein should be used to obtain the density level (ie,> 650 g / l) required by low-dose, compact, modern detergent products. For example, the spray-dried granules of a tower can be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules and / or by subjecting them to one or more high-speed mixer / densifiers. A high speed mixer / densifier suitable for this purpose is a device marketed under the trade name "Lodige CB 30" or "Lódige CB 30 Recycler" which comprises a static cylindrical mixing drum having a central rotation arrow with mixing blades / cut mounted on it. During use, the ingredients for the detergent composition are introduced into the drum and the arrow / blade assembly is rotated at speeds in the range of 100-250 rpm to provide uniform mixing / densification. See Jacobs, patent of E.U.A. 5,149,455, issued September 22, 1992, and patent of E.U.A. 5,565,422, issued October 15, 1996 to Del Greco et al. Another apparatus of this type includes devices marketed under the trade name "Shugi Granulator" and under the trade name "Drais K-TTP 80. Another step of the process that can be used to densify spray-dried granules involves treating the dried granules by spraying in a moderate speed mixer / densifier Equipment such as that marketed under the name "Lódige KM" (Series 300 or 600) or "Lodige Ploughshare" mixer / densifiers are suitable for this process step. Said equipment is operated typically at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer / densifier is approximately 0.1 to 12 minutes conveniently measured by dividing the weight of the constant state mixer / densifier between production (eg, Kg / hr). Other useful equipment includes the device that is available under the trade name "Drais K-T 160". This process step employing a moderate speed mixer / densifier (eg Lodige KM) can be used as such or sequentially with the aforementioned high speed mixer / densifier (see Lódige CB) to achieve density desired. Other types of apparatus for making granules useful herein include the apparatus described in the U.S.A. 2,306,898 of G.L. Heller, December 29, 1942. t i a i A - "Although it may be more appropriate to use the high speed mixer / densifier followed by the low speed mixer / densifier, the reverse sequential mixer / densifier configuration can also be used. One or a combination of various parameters including residence times in mixer / densifiers, equipment operating temperatures, temperature and / or composition of the granules, the use of auxiliary ingredients such as liquid binders and flow aids, can be used to optimize the densification of the spray-dried granules in the process of the invention. By way of example, see the procedures in Appel et al, U.S. Pat. 5,133,924, issued July 28, 1992; Delwel et al, patent of E.U.A. 4,637,891, issued January 20, 1987; Kruse et al, patent of E.U.A. 4,726,908, issued February 3, 1988 and Bortolotti et al, patent of E.U.A. 5,160,657, issued November 3, 1992. In those situations in which particularly hot-sensitive or highly volatile detergent ingredients are to be incorporated into the final detergent composition, processes which do not include spray-drying towers are preferred. The formulator can eliminate the spray drying step by feeding, either in a continuous or intermittent mode, starting detergent ingredients directly into the commercially available mixing equipment. A particularly preferred embodiment involves charging a surfactant paste and an anhydrous material in a high speed mixer / densifier (eg Lodige. , ..? t ± m i. m, = ^ ß .t ,. * .... ¡¡ _ .. . .- - - ~, .. -a í ?. Í.
CB) followed by a moderate speed mixer / densifier (see Fig. KM) to form high density detergent agglomerates. See Capeci et al, patent of E.U.A. 5,366,652, issued November 22, 1994 and Capeci et al, patent of E.U.A. 5,486,303, issued January 23, 1996. Optionally, the liquid / solids ratio of the starting detergent ingredients in said process can be selected to obtain high density agglomerates that are freer and crisper. See Capeci et al, patent of E.U.A. 5,565,137, issued October 15, 1996. Optionally, the process may include one or more undersized recycle streams produced by the process that are fed back into the mixer / densifier for agglomeration or additional buildup. The oversized particles produced by this process can be sent to a grinding apparatus and then fed back to the mixing / densification equipment. These additional recycling process steps facilitate the agglomeration by accumulation of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g / l). . See Capeci et al, patent of E.U.A. 5,516,448, issued May 14, 1996 and Capeci et al, US patent. 5,489,392, issued February 6, 1996. Other suitable methods that do not require the use of spray drying towers are described in Bollier et al, U.S. .._, - > > . ^ ^ L.L 4,828,721, issued on May 9, 1989; Beerse et al, patent of E.U.A. 5,108,646, issued April 28, 1992; and Jolicoeur, patent of E.U.A. 5,178,798, issued January 12, 1993. In another embodiment, a high density detergent composition is used using a fluidized bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous suspension (typically 80% solids content) and sprayed in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this method may optionally include the step of mixing the suspension using the aforementioned Lódige CB mixer / densifier or a "Flexomix 160" mixer / densifier., available from Shugi. The fluidized bed or moving beds of the type available under the trade name "Escher Wyss" can be used in such processes. Another suitable method that can be used in the present invention involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (eg, sodium carbonate) and optionally other detergent ingredients into a high speed mixer / densifier for forming particles containing a partially or fully neutralized anionic surfactant salt and the other detergent ingredients. Optionally, the content in the high speed mixer / densifier can be sent to a moderate speed mixer / densifier (eg Lodige KM) for a i.; ? to additional mixing resulting in the finished high-speed detergent composition. See Appel et al, patent of E.U.A. 5,164,108, issued November 17, 1992. Optionally, the high density detergent compositions according to the invention can be produced by mixing conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (eg, a weight ratio of 60:40 from granules to agglomerates) produced by one or a combination of the procedures described herein. See patent of E.U.A. 5,569,645, issued October 29, 1996 to Dinniwell et al. Additional auxiliary ingredients such as enzymes, perfumes, brighteners and the like can be sprinkled or mixed with the agglomerates, granules or mixtures thereof produced by the processes described herein.
Laundry Washing Method The laundry washing methods of the present invention typically comprise treating the laundry with an aqueous washing solution in a washing machine having dissolved or supplied therein an effective amount of a washing detergent composition in a machine according to the present invention. with the invention For an effective amount of the detergent composition is meant from 40 g to 300 g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and in volumes of wash solution commonly used in conventional machine washing methods. As mentioned, surfactants are used herein in detergent compositions, preferably in combination with other detersive surfactants, at levels that are effective to achieve at least a directional improvement in cleaning performance. In the context of a composition for washing fabrics, said "use levels" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the wash water, the volume of the wash water and the type of washing machine.
Packaging for compositions Commercially sold executions of the compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastic materials and any suitable laminates. A preferred packaging embodiment is described in European application No. 94921505.7. The compositions of the present invention can be packaged with a variety of suitable detergent packages known to those skilled in the art, the liquid compositions preferably being packaged in conventional detergent plastic bottles. The following examples are illustrative of the present invention, but are not intended to limit or otherwise define its scope. All tt .i. -. to n,? .a-A-t, * -.
Parts, percentages and ratios used here are expressed as weight percent unless otherwise specified.
EXAMPLES EXAMPLE 1 Preparation of C? H? 3E07B? 7-2-ethylhexylacetal Neodol 1-7 (20.00 g, 41.6 mmol) is placed in a 500 ml three neck round neck flask, equipped with a heating mantle, magnetic stirrer, thermometer internal and inlet for argon and dried under vacuum at 75 ° C. After releasing the vacuum with argon, metallic sodium (0.05 g, 2.1 mmol) is added and the mixture is stirred replaced 1 hour at 120 ° C. After increasing the reaction temperature to 140 ° C, 1,2-epoxybutane (6.00 g, 83.2 mmol) is added dropwise over 30 minutes. After the addition is complete, the mixture is stirred for an additional 1 hour at 140 ° C. The solution is cooled to 90 ° C and neutralized with concentrated HCl. After removing the water and the last traces of 1,2-epoxybitan under vacuum and cooling to the environment, methylene chloride (200 ml) and 2-ethylhexyl vinyl ether (19.49 g, 124.7 mmol) are added. The mixture is cooled to 0 ° C and pyridinium p-toluenesulfonate (0.42 g, 1.7 mmol) is added. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at ^^ if ambient temperature. After diluting with diethyl ether (200 ml), the mixture is washed twice with saturated sodium bicarbonate and the organic layer is dried with sodium sulfate / potassium carbonate. The product was concentrated by rotary evaporation and dried under vacuum in the presence of potassium carbonate to give a yellow liquid.
EXAMPLE 2 Examples 2 (a) to (i) are illustrative of some of the possible 10 catalysts, treatment options and relative amounts of starting materials that can be used in the present invention.
EXAMPLE 2fa) Preparation of CQ / nH? G /? 3EOfl-cyclohexyl acetal Neodol 91-8 (20.00 g, 39.1 mmol) is placed in a 250 ml three neck round neck flask equipped with a heating blanket, magnetic stirrer, thermometer internal and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (100 ml) and cyclohexylvinyl ether (5.43 g, 43.01 mmol) are added. The mixture is cooled to 0 ° C and enter pyridinium p-toluensulfonate (0.43 g, 1.6 mmol) into the flask. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at room temperature. The product mixture is then washed twice with saturated sodium bicarbonate and the organic layer is dried over sodium carbonate, concentrated by rotary evaporation and subsequently separated under vacuum at 60 ° C (OJ mmHg) in the presence of potassium carbonate. to produce a liquid.
EXAMPLE 2fb) Preparation of Cg /? H? G / 73EO »-cyclohexylacetal Neodol 91-8 (20.00 g, 39.1 mmol) and poly (4-vinylpyridinium) p-toluenesulfonate (0.43 g) are introduced into a 250 ml three-necked round neck, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, cyclohexyl vinyl ether (4.94 g, 39.1 mmol) is added. The mixture is heated at 70-95 ° C overnight. The product mixture is filtered to produce a liquid. r? JE A r A I. »^ A - ^ ^ m * ^ t-mji-.,, .fcA.i ... fcJ.
EXAMPLE 2fc) Preparation of CQ / HiQ /? 3EO «-cyclohexylacetal Neodol 91-8 (20.00 g, 39.1 mmol) and poly (4-vinylpyridinium) p-toluenesulfonate (0.43 g) are introduced into a round neck flask of three 250 ml necks, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, cyclohexyl vinyl ether (4.94 g, 39.1 mmol) is added. The mixture is heated at 70-95 ° C overnight. The product mixture is separated from the catalyst by centrifugation to produce a liquid.
EXAMPLE 2 (d) Preparation of Cg /? Hifl / 23EOa-cyclohexyl acetal Neodol 91-8 (20.00 g, 39.1 mmol) and poly (4-vinylpyridinium p-toluenesulfonate) (0.43 g) are introduced into a 250 ml three neck round neck flask ml, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum to ? - t? A. fc s »> 75 ° C. After cooling to room temperature and releasing the vacuum with argon, cyclohexyl vinyl ether (4.94 g, 39J mmoles) is added. The mixture is heated at 70-95 ° C overnight. The product mixture is washed with 20% potassium carbonate solution, dried and filtered to produce a liquid. EXAMPLE 2fe) Preparation of C »/? NHi7 / ?? EOft-cyclohexyl acetal Ethoxylated alcohol C8 / 10H17 / 21EO8 (20.00 g, 40.2 mmol) and poly (4-vinylpyridinium) chloride (2.0 g) are introduced into a three-necked round-bottomed flask necks of 250 ml, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, cyclohexyl vinyl ether (5.07 g, 40.2 mmol) is added. The mixture is heated at 70-95 ° C overnight. The product mixture is filtered to produce a liquid.
EXAMPLE 2 (fí > Preparation of CQ / nH g /? 3E08-cyclohexyl acetal Neodol 91-8 (20.00 g, 39J mmoles) and poly (4-vinylpyridinium p-toluenesulfonate) (7.82 g) are introduced into a 250 ml three neck round neck flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon , acetone (150 ml) and cyclohexyl vinyl ether (4.94 g, 39J mmoles) are added.The mixture is stirred for 3 days, filtered and concentrated by rotary evaporation to produce a liquid.
EXAMPLE 2 (q) C rfCHatoßCr > N JJD Preparation of CQ / nHigmEOn-cyclohexyl acetal Neodol 91-8 (20.00 g, 39.1 mmol) is placed in a 250 ml three neck round neck flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (100 ml) and cyclohexylvinyl ether (4.84 g, 38.4 mmol) are added. The mixture is cooled to 0 ° C and pyridinium p-toluenesulfonate (0.39 g, 1.5 mmol) is introduced into the flask. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at L -M & ^ i.- room temperature. The product mixture is then washed twice with saturated sodium bicarbonate and the organic layer is dried over sodium carbonate, concentrated by rotary evaporation and subsequently separated under vacuum at 60 ° C (OJ mmHg) in the presence of potassium carbonate. to produce a liquid.
EXAMPLE 2fh) Preparation of Ca /? H? G /? 3EOft-cyclohexyl acetal Neodol 91-8 (20.00 g, 39.1 mmol) is placed in a 250 ml three neck round neck flask, equipped with a heating mantle, magnetic stirrer, Internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature, cyclohexyl vinyl ether (5.04 g, 39.9 mmol) is added. P-Toluenesulfonic acid monohydrate (0.112 g, 0.59 mmol) is added to the mixture and stirred to dissolve. An exotherm is observed starting at 22 ° C and ending at 30 ° C, with the development of a precipitate. After 16 minutes of reaction time, the pH of the reaction is adjusted to > 7 with triethanolamine, filtered and then separated in a Kugeirohr oven (50 ° C, 0.1 mm Hg) to produce a quantitative amount of an almost colorless liquid. fifteen EXAMPLE 2 (i) CHsíCHjJrßCHzO < - Preparation of Cg / nHigmEOg-cyclohexyl acetal Neodol 91-8 (900.0 g, 1.76 mmol) is placed in a 3-liter three-necked round bottom flask, equipped with a heating mantle, mechanical stirrer, internal thermometer and vacuum adapter / Argon collection. The contents are dried under vacuum at 80 ° C for 30 minutes. A portion of dry 91-8 Neodol (20 g) is set aside after the contents are cooled to room temperature. Then cyclohexyl vinyl ether (217.82 g, 1.73 mmol) is added to the reaction mixture. The reagents are cooled to approximately 10 ° C, at which point the methanesulfonic acid (1.80 ml) and the 20 g portion of Neodol set aside are combined and added to the reaction mixture by syringe, in the sub- surface in a portion. The exotherms of the reaction mixture are controlled with an ice bath at 22 ° C. After 1 hour, the mixture is quenched with 15% sodium carbonate solution (35 ml). The mixture is placed under vacuum by separation in a Kugeirohr oven (25 ° C, 0.1 mm Hg) for 10 minutes. The product is filtered to produce a quantitative amount of an almost colorless liquid.
¿A, ,, í .í. ». J? i l, Ú EXAMPLE 3 Preparation of Cg / nH? G / 73EOfl-benzylacetal The procedure of example 2 (i) is repeated substituting Neodol 91-8 for Neodol 1-7.
EXAMPLE 4 Preparation of Cg / nHi9 / 2aEOg-benzylacetal The procedure of example 3 is repeated substituting the cyclohexyl vinyl ether for benzyl vinyl ether.
EXAMPLE 5 T? yl. Preparation of C? E07-fer-amylacetal Neodol 1-7 (20.00 g, 41.6 mmol) is placed in a 1000 ml three-necked round bottom flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (200 ml) and terpentylvinyl ether (14.24 g, 124.7 mmol) are added. The mixture is cooled to 0 ° C and pyridinium p-toluenesulfonate (0.42 g, 1.7 mmol) is added. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at room temperature. After being diluted with diethyl ether (200 ml), the mixture is washed twice with saturated sodium bicarbonate and the organic layer is dried with sodium sulfate / potassium carbonate. The product is concentrated by rotary evaporation and dried under vacuum in the presence of potassium carbonate to produce an almost colorless liquid.
EXAMPLE 6 Preparation of C ?? / β sH9. ^ EOi9-2-ethylhexylacetal The procedure of example 2 (i) is repeated substituting cyclohexyl vinyl ether for 2-ethylhexyl vinyl ether and Neodol 1-7 for Tergitol 15-S-12. &3Í a ^ d. i l ': * ¿,, £ £ "1 * 1 EXAMPLE 7 Preparation of Cg / nEOaPO? -fer-amylacetal The procedure of Example 1 is repeated substituting 1, 2-epoxybutane for propylene oxide, 2-ethylhexylvinyl ether for terilvinyl ether and Neodol 1-7 for Neodol 91-8.
EXAMPLE 8 Preparation of Cn /? SH23 / 3? EOgP? 9-cyclohexyl acetal The procedure of example 1 is repeated substituting 1, 2-epoxybutane for propylene oxide, 2-ethylhexylvinyl ether for cyclohexylvinyl and Neodol 1-7 for Tergitol 15-S- 9.
EXAMPLE 9 The procedure of example 1 is repeated substituting 2-ethylhexylvinyl ether for cyclohexylvinyl ether and Neodol 1-7 for Neodol 25-9.
EXAMPLE 10 Preparation of Cg / nEQfl-octadecylacetal The procedure of example 2 (b) is repeated substituting cyclohexyl vinyl ether for octadecyl vinyl ether and Neodol 1-7 for Neodol 91-8.
EXAMPLE 11 Preparation of CnEOg-cyclohexyl acetal Neodol 1-7 (50.00 g, 104.0 mmol) is placed in a 1000 ml three-necked round bottom flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (500 ml) and cyclohexylvinyl ether (6.55 g, 51.9 mmol) are added. The mixture is cooled to 0 ° C and pyridinium p-toluenesulfonate (1.04 g, 4.2 mmol) is introduced into the flask. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at room temperature. The product mixture is then washed twice with saturated sodium bicarbonate and the organic layer is dried with magnesium sulfate, concentrated by rotary evaporation and then separated under vacuum at 60 ° C (OJ mmHg) to produce a red liquid. coffee.
EXAMPLE 12 Preparation of C? /? SEO ??-ethyl acetal Neodol 25-12 (76.61 g, 104.0 mmol) is placed in a 1000 ml three-necked round bottom flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and inlet for argon and dried under vacuum at 75 ° C. After cooling to room temperature and releasing the vacuum with argon, methylene chloride (500 ml) and ethyl vinyl ether (7.50 g, 104.0 mmol) are added. The mixture is cooled to 0 ° C and pyridinium p-toluenesulfonate (1.04 g, 4.2 mmol) is introduced into the flask. The mixture is stirred first for 4 hours at 0 ° C and then for 18 hours at room temperature. The product mixture is then washed twice with saturated sodium bicarbonate and the organic layer is dried with magnesium sulfate, concentrated by rotary evaporation and then separated under vacuum at 60 ° C (OJ mmHg) to produce a red liquid. coffee. EXAMPLE 13 CH3 (CH2)? O.i4? (20), - «- Preparation of C? / IñH23 / 3? EOifi-cyclohexallacetal Tergitol 15-S-15 (100.0 g, 193.8 mmol) is placed in a 250 ml three neck round bottom flask, equipped with a heating mantle, magnetic stirrer, internal thermometer and vacuum adapter / argon collection. The contents are dried under vacuum at 80 ° C for 10 minutes. A portion of the dried Tergitol 15-S-15 (2 g) is set aside after the contents are cooled to room temperature. Then cyclohexyl vinyl ether (24.21 g, 191.9 mmol) is added to the reaction mixture. The reagents are cooled to approximately 15 ° C, at which point the methanesulfonic acid (0.28 g, 2.9 mmol) and the 2 g portion of Tergitol 15-S-15 set aside are combined and added to the reaction mixture. by syringe, on the sub-surface in a portion. The reaction mixture exotherms to 40 ° C. After 5 minutes, the pH of the reaction is adjusted to >; 7 with 15% sodium carbonate. The mixture is placed under vacuum by separation in a Kugeirohr oven (50 ° C, 0.1 mm Hg) for 10 minutes. The product is filtered to produce a quantitative amount of an almost colorless liquid.
The following examples are illustrative of the present invention but are not intended to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise specified. In the following examples, the abbreviations for the various ingredients used for the compositions have the following meanings.
LAS: Linear sodium C12 alkylbenzene sulfonate MBASx Primary alkylated sulfate in the middle region of its chain (average total carbon = x) MBAEX xS ^ z- Ethoxylated alkyl ethoxylated (average EO = x) branched primary in the middle region of its chain (carbons average total aquyl = z), MBAEX sodium salt: Branched primary ethoxylated alkyl in the middle region of its chain (average total aquiloal carbon = x) (average EO = 8) TFAA: C16-C18 alkyl N-methylglucamide CxyEzS: C? XC? Branched alkyl and sodium condensate with z moles of ethylene oxide CxyFA: Fatty acid of C? XC? And CxyEz: A branched primary alcohol of C? XC? And condensed with an average of z moles of ethylene C24 N-Me-N-methylglucamide of C12-C14 alkyl Glucamide: ti m 2 Go í i .fca \ r¿ J & £ & CxAPA: Alkylamidopropylamide Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with an average particle size between 200 μm and 900 μm Citrarto: Trisodium citrate dihydrate of 86.4% activity with particle size distribution between 425 μm and 850 μm Protease: Proteolytic enzyme of activity 4KNPU / g sold by NOVO Industries A / S under the trade name Savinase Cellulase: Cellulite enzyme of activity 1000CEVU / g sold by NOVO Industries A / S under the trade name Carezyme Amylase: Amylolytic enzyme activity 60KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T Lipase: Activity lipolytic enzyme 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase Endolase: Activity endoglucanase enzyme 3000kLU / g sold by NOVO Industries A / S PB1: Anhydrous sodium perborate bleach of nominal formula NaB02.H202 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt DTPMP: Diethylenetriaminpenta (methylene phosphonate), marketed by Monsanto under the trade name Dequest 2060 MEA: Monoethanolamine PG: Propanediol EtOH: Ethanol Brightener 1: 4,4'-bis (2-sulphotryryl) biphenyl disodium Brightener 2: 4,4, -bis (4-anilino-6-morpholino-1 , Disodium 3,5-triazin-2-yl) amino) stilbene-2,2'-disulfonate Foam-based controller: polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer silicone as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 NaOH: Sodium hydroxide solution DTPA: Diethylenetriaminpentaacetic acid NaTS: Sodium toluene sulfonic acid Fatty acid: C12-C 14 fatty acid (C12 / 14) Fatty acid (TPK): Acid palm kernel fatty acid Fatty acid (RPS): Rapeseed fatty acid Borax: Sodium tetrahydrate decahydrate PAA: Polyacrylic acid (MW = 4500) PEG: Polyethylene glycol (MW = 4600) MONTH: Alkylmethyl ester sulfate SAS: Alkylsulfate secondary NaPS: Paraffinsulfonate sodium C45AS: C14-C15 linear sodium alkylsulfate CxyAS: C? XC? And sodium linear alkylsulfate (or other salt if specified) AQA: R2.N + (CH3) 2 ((C2H40) yH) z with R2 = C8 -C? 4 STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Nai2 (Al? 2Si02) i2. 27H2O, which has a primary particle size in the range of OJ to 10 microns NaSKS-6: Crystalline layered silicate of the formula d-Na2Si2? S Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm Silicate: Amorphous sodium silicate (ratio of 2.0 Si02: Na20) Sulfate: Anhydrous sodium sulfate PAE: Ethoxylated tetraethylenepentamine PIE: Ethoxylated polyethyleneimine PAEC: Ethoxylated dihexylenetriamine quaternized with methyl MA / AA: Copolymer of maleic acid / acrylic acid 1: 4 with an average molecular weight of approximately 70,000 CMC: Sodium carboxymethylcellulose Protease: 4KNPU / g activity proteolytic enzyme sold by NOVO Industries A / S under the trade name Savinase Cellulase: Cellulite enzyme of activity 1000CEVU / g sold by NOVO Industries A / S under the trade name Carezyme yt -i .í t ru? ...., r .r Amylase: Activity amylolytic enzyme 60KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T Lipase: Activity lipolytic enzyme 100kLU / g sold by NOVO Industries A / S under the trade name Lipolase Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H202 NaDCC: Sodium dichloroisocyanurate TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in HEXP dextrin soluble polymer: 1, 1-hydroxyetho-diphosphonic acid SRP 1: Sulfobenzoyl blocked end esters with oxyethyleneoxy and terephthaloyl base structure SRP 2: Sulphonated ethoxylated terephthalate polymer SRP 3: Ethoxylated terephthalate polymer blocked with methyl Isofol 16: Commercial name of Condea for Guerbet alcohols From C16 (average) CaCl2: Calcium chloride MgCl2: Magnesium chloride , j, -, -...,, .-. Jr ^ y, - - ,. 'iUt' i '-.-Á.-, DTPA: Diethylenetriaminpentaacetic acid EXAMPLES 14 TO 14E Non-aqueous liquid laundry detergent compositions Non-limiting examples of non-aqueous liquid laundry detergent containing bleach is prepared in the following manner.
Preparation of LAS powder to be used as a surfactant Sodium C12 linear alkylbenzene sulfonate (NaLAS) is processed into a powder containing two phases. One of these phases is soluble in the non-aqueous liquid detergent compositions of the present invention and the other phase is insoluble. It is the insoluble fraction that serves to add structure and suspension capacity of particles to the non-aqueous phase of the compositions of the present invention. The NaLAS powder is produced by carrying a suspension of NaLAS in water (approximately 40-50% active) combined with dissolved sodium sulphate (3-15%) and hydrotrope, sodium sulfosuccinate (1-3%). Hydrotrope and sulfate are used to show the characteristics of dry powder. A drum dryer is used to dry the suspension in a flake. When the NaLAS is dried with sodium sulfate, two distinct phases are created within the leaflet. The insoluble phase creates a particle network structure l? r? l. small aggregates (0.4-2 um) that allow the finished non-aqueous detergent product to stably suspend solids. The NaLAS powder prepared in accordance with the example has the following constitution shown in Table I.
TABLE I Powder LAS The non-aqueous laundry heavy duty liquid laundry detergent compositions comprising the blocked nonionic surfactants of the present invention are presented below. hAt .Á-. JJ? Í. í &i js a. J ± I L The resulting compositions are laundry detergents Heavy-duty anhydrous, stable liquids that provide excellent mixing speed with water as well as good removal performance of stains and dirt when used in laundry operations of fabrics normal.
EXAMPLE 15 Liquid compositions for manual dishwashing The following examples further illustrate the present invention with respect to the liquid for manual dishwashing.
Example 15: Ingredient% in this range (% by weight) Non-ionic examples of either 5.0 1-20 11 0 12 MBAE2S? 5 2.0 0.5-10 Ammonium alkylsulfate of C12-13 7.0 2-35 Etoxysulfate (1) of Ci2 -C? 4 20.5 5-35 Cocoamine oxide 2.6 2-5 Betaine / Tetronic 704® ** 0.87- .10 0-2 (mixture) Ethoxylated alcohol EgdeCg-n 1.0 0.5-10 Ammonium xylene sulfonate 4.0 1-6 IÍJLA - Ethanol 4.0 0-7 Ammonium Citrate 0.06 0-1.0 Magnesium Chloride 3.3 0-4.0 Calcium Chloride 2.5 0-4.0 Ammonium Sulfate 0.08 0-4.0 Perfume 0J8 0-0.5 Maxatase® Protease 0.50 0-1.0 Water and Components lower the rest 'Cocoalkylbetaine EXAMPLES 16 TO 20 Compositions of? shampoo Number of eiemp lo Component 16 17 18 19 20 Laureth-2-ammonium sulfate 5 3 2 10 8 Ammonium lauryl sulfate 5 5 4 5 8 Nonionic of example 3 2 0 0 4 7 Non ionic of example 6 0 3 0 0 0 Non-ionic example 9 0 0 4 1 0 MEA of cocamide 0 0.68 0.68 0.68 0.8 PEG 14M 0.1 0.35 0.5 0.1 0 Cocoamidopropylbetaine 2.5 2.5 0 0 1.5 Cetyl alcohol 0.42 0.42 0.42 0.5 0.5 Stearyl Alcohol 0.18 0.18 0.18 0.2 0.18 Ethylene glycol distearate 1.5 1.5 1.5 1.5 1.5 Dimeticone1 1.75 1.75 1.75 1.75 2.0 Perfume solution 0.45 0.45 0.45 0.45 0.45 DMDM hydantoin 0.37 0.37 0.37 0.37 0.37 Color solution (ppm) 64 64 64 64 64 Water and minor components sufficient amount for 100% 1. Dimethicone is a mixture in a weight ratio of 0 (gum / 60 (fluid) of dimethicone rubber SE-76 available from General L L ±? -Á Electric Silicones Division and a dimethicone fluid that has a viscosity of 350 centistokes.
EXAMPLE 21 TO 36: Granular laundry detergents The following laundry detergent compositions were prepared according to the invention: t sA d »A *.? *. £ &&&**. ~ i A. ^ »^,. -? The following laundry detergent compositions were prepared according to the invention: 10 fifteen The following laundry detergent compositions were prepared according to the invention: fi iaiiitwmr t m, &., fc-g I ^ í EXAMPLES 37 TO 44: Hard surface cleaners The following compositions were made by mixing the ingredients listed in the proportions listed. These compositions are They were used in pure form to clean marble and were diluted to clean lacquered wood floors. Excellent cleaning performance was observed and surface security. 37 38 39 40 41 42 43 44 Non ionic of 3.0 - 1.0 - 3.2 - - - example 7 Non ionic of 3.0 2.0. . 4.0 8.0 example 1 Non-ion 2.0 3.2 3.2 4.0. example 9 C23E3 1.0 1.0 1.5 1.3 1.3 1.5 3.0 3.5 C24E21 2.0 2.0 2.5 1.9 1.9 2.0 5.0 6.0 NaPS 2.0 1.5 1.2 1.2 1.0 1.7 3.0 2.5 NaTS 1.2 3.0 2.2 2.0 2.0 1.5 4.0 5.0 MgS04 0.20 0.9 0.30 0.50 1.3 2.0 1.0 3.0 Citrate 0.3 1.0 0.5 0.75 1.8 3.0 1.5 6.0 NaHC03 0.06 0.1 - 0J - 0.2 - - Na2HP04 - - 0.1 - 0.3 - - - Na2H2P207 - - - - - - 0.2 0.5 PH 8.0 7.5 7.0 7.25 8.0 7.4 7.5 7.2 Water and sufficient quantity for 100% components minors Isa j ^ i £ -sü ^? ¿^ ».? EXAMPLE 45 compositions for automatic dishwashing Ingredients% by weight AB Sodium Tripolyphosphate (STPP) 24.0 45.0 Sodium Carbonate 20.0 13.5 Hydrated Silicate 2.0r 15.0 13.5 Nonionic Surfactant1 3.0 3.0 Amine Oxide of C 1.0 1.0 Polymer2 4.0 - Protease (4% active) 0.83 0.83 Amylase ( 0.8% active) 0.5 0.5 Perborate monohydrate (15.5% 14.5 14.5 active AvO) 3 Cobalt catalyst4 0.008 - Dibenzoyl peroxide (18% actio) 4.4 4.4 Water, sodium sulfate, components the rest the various rest 1 nonionic surfactant according to example 1. 2 terpolymer selected from 60% acrylic acid / 20% maleic acid / 20% ethyl acrylate, or 70% acrylic acid / 10% maleic acid / 20% of ethyl acrylate. 3 The AvO level of the previous formula is 2.2%. 4 Pentaaminoacetatecobalt Nitrate (III) prepared as described earlier; it can be replaced by MnTacN.
The following examples further illustrate ADD compositions with phosphate detergent builder containing particles of bleach / enzyme, but does not intend to limit itself to them. These compositions are suitable for use in the methods of the present invention. All the percentages observed are by weight of the finished compositions, different from the perborate component (monohydrate), which is listed as AvO.
EXAMPLES 46-47 Ingredients% by weight 46 47 STPP 30.0 32.0 Na2C03 30.5 20.5 Silicate 2 R (Si02) 8.0 4.0 Catalyst1 0.008 0.004 Savinase ™ 12T - 1.1 Protease D 0.9 - Perborate (AvO) 5.0 0.7 Polymer2 4.0 - Dibenzoyl peroxide 0.2 0.15 Paraffin 0.5 0.5 Benzotriazole EYE 0.3 Amine oxide C14 0.5 0.5 Nonionic surfactant3 2.0 2.0 Sodium sulphate, moisture the rest 1 Pentaaminoacetatecobalt nitrate (III); it can be replaced by MnTacN. 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers. 3 Nonionic surfactant according to example 7 In the compositions of Examples 46 and 47 respectively, the catalyst and enzymes are introduced into the compositions as particles Mixed 200-2400 microns, which are prepared by spray coating, fluidized bed granulation, maruization, formation of «, ¿+ .itsá-4 pills or flaking / crushing operations. If desired, protease and amylase enzymes can be formed separately in their respective mixed catalyst / enzyme particles for stability reasons, and these separate compositions are added to the compositions.
The following examples illustrate granular compositions of ADD with chlorine bleach suitable for use in the methods of the present invention.
EXAMPLES 48-49 10 Ingredients% by weight 48 49 STPP 25 31 Na2C03 23.0 15.0 Silicate 2 R (Si02) 17.5 25.0 Hypochlorite 1.0 3.0 Polymer1 2.0 - Dibenzoyl peroxide - 0.15 15 Paraffin 1.0 1.0 Amine oxide C 0.5 1.0 Nonionic surfactant2 2.0 3.0 Sulphate of sodium, moisture the rest 1 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers. 3 Nonionic surfactant agent according to example 8.
The following examples further illustrate ADD liquid-gel compositions suitable for use in the methods of the present invention.
EXAMPLES 50-51 Ingredients% by weight 50 51 STPP 32.0 25.0 Na2C03 0.7 2.0 Silicate 2 R (Si02) 0.3 1.0 Savinase ™ 12T 2.0 1.0 Termamyl ™ 1.4 0.5 Perborate (AvO) 3.5 - Amine C oxide? 0.8 0.8 Nonionic surfactant1 3.5 3.5 Sodium sulfate, moisture the rest 1 Nonionic surfactant according to example 3. The following examples further illustrate compositions ADD rinsing aids for use in the methods herein invention.
EXAMPLES 52-53 Ingredients% by weight 52 53 Citric acid 10.0 15.0 Ethanol 5.0 10.0 Acid HEDP1 1.0 0.7 Sodium cumenesulfonate 15.0 10.0 Polymer2 - 1.0 Amine oxide C 2.0 0.5 Nonionic surfactant3 8.0 8.0 Nonionic surfactant4 6.0 - Moisture the rest 1-Hydroxyethylidene-1,1-diphosphonic acid. í'k &Á..A, *. .t. * ~~~., 2 Polyacrylate or Acusol 480N or polyacrylate / polymethacrylate copolymers. 3 Nonionic surfactant according to example 1. 4 Nonionic surfactant according to example 5.
The following examples further illustrate compositions of ADD tablets suitable for use in the methods of the present invention.
EXAMPLES 54-55 Ingredients c Weight by weight 54 55 STPP 48.0 30 Na2C03 15.0 25.0 Silicate 2 R (Si02) 4.0 8.0 Catalyst1 0.008 0.004 Savinase ™ 12T - 1.0 Termamyl ™ 0.6 0.5 Perborate (AvO) 10.0 15.0 Polymer 2.0 2.0 2.0 Dibenzoyl peroxide 0.2 0.15 Paraffin 1.0 1.0 Benzotriazole 0.5 0.5 Amine oxide Cu 1.0 1.0 Nonionic surfactant3 3.0 3.0 Sodium sulphate, moisture the rest 1 Pentaaminoacetatecobalt nitrate (III); can be replaced by MnTacN. 2Polyacrylate or Acusol 480N or copolymers of polyacrylate / polymethacrylate. 3 Nonionic surfactant according to example 5. il l

Claims (21)

NOVELTY OF THE INVENTION CLAIMS
1. - A detergent composition comprising: (a) 0.01% a 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group which consists of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C to C3 or R2 has from 6 to 30 carbon atoms; and (b) from 0.1% to 99% by weight of the composition of an adjunct ingredient.
2. - An auxiliary automatic dishwashing rinse composition comprising: (a) from 0.01% to 50% by weight of the surfactant composition, wherein said surfactant comprises a poly (oxyalkylated) alcohol surfactant blocked with ether having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; carbon; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms; and (b) from 0.1% to 99% by weight of the composition of an adjunct ingredient; and (c) from 0.1% to 99% by weight of the composition of an aqueous liquid vehicle.
3. A bleaching composition comprising: (a) from 0.01% to 50% by weight of the surfactant composition, wherein said l, ¡? ik? surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated hydrocarbon radicals, substituted or unsubstituted, aliphatic or aromatic having from 1 to 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (i) aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; provided that when R2 is (ii) then either at least one of R1 is different from alkylene of C2 to C3 or R2 has from 6 to 30 carbon atoms; and (b) from 0.1% to 99% by weight of the composition of an adjunct ingredient; and (c) from 0.1% to 99% by weight of the composition of a bleaching system.
4. A detergent composition comprising: (a) from 0.01% to 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group consisting of straight or branched hydrocarbon radicals, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic having from 1 to 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C2 alkylene in any given molecule; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (i) aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; (b) from 0.1% to 99% by weight of the composition of an amine oxide co-surfactant; and (c) from 0.1% to 99% by weight of the composition of an adjunct ingredient.
5. A detergent composition comprising: (a) from 0.01% to 50% by weight of the surfactant composition, wherein said surfactant comprises a poly (oxyalkylated) alcohol surfactant blocked with ether having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any molecule r- WAlß Í «*» fr? »I». J. * rmr? Ür, i. . . ^ r .... Dadaist; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; (b) from 0.1% to 99% by weight of the hydrophobic surfactant co-agent composition, wherein said hydrophobic co-surfactant has either a HLB value less than or equal to 12 or a Kraft temperature greater than about 20 ° C, and (c) from 0.1% to 99% by weight of the composition of an adjunct ingredient.
6. A detergent composition comprising: (a) from 0.01% to 50% by weight of the surfactant composition, wherein said surfactant comprises an ether-blocked poly (oxyalkylated alcohol) surfactant having the formula: RO (R10) xCH (CH3) OR2 wherein R is selected from the group consisting of aliphatic or aromatic linear or branched, saturated or unsaturated hydrocarbon radicals, substituted or unsubstituted, having from 1 to 30 carbon atoms; R1 may be the same or different and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; x is a number from 1 to 30; and R2 is selected from the group consisting of: (i) a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms; and (ii) hydrocarbon radicals -? .¿.J ~ l, .am tA.I¿ ..? .. l. **. ~. l. . »| Rt | "| H" ~, - - m m ~ -.- - - ... . > . - * - »-. -. ».. ~. ^ .. r ^. * .. «-. «. üArl.? aliphatic or aromatic, linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic having from 1 to 30 carbon atoms; (b) from 0.1% to 99% by weight of the composition of an adjunct ingredient; wherein said composition comprises less than 1% dialkoxylated acetal of the formula: RO (R10) xCH (CH3) (OR1) xOR wherein each x is an independently selected number from 1 to 30; and R and R1 are defined as before.
7. The composition according to any of claims 1-6, further characterized in that R is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical, substituted or unsubstituted, having from 1 to 20 carbon atoms.
8. The composition according to any of claims 1-7, further characterized in that R is a linear or branched, saturated aliphatic hydrocarbon radical having from 4 to 18 carbon atoms.
9. The composition according to any of claims 1-8, further characterized in that R2 is a hydrocarbon radical of the formula: C (CH3) 2R3 wherein R3 is selected from the group consisting of linear aliphatic or aromatic hydrocarbon radicals or branched, saturated or unsaturated, substituted or unsubstituted having from 1 to 30 carbon atoms.
10. The composition according to any of claims 1-8, further characterized in that R 2 is a substituted or unsubstituted heterocyclic ring of 4 to 8 members containing from 1 to 3 heteroatoms. 11. The composition according to any of claims 1-8 and 10, further characterized in that said heterocycle is selected from the group consisting of:
A ~ "^ - ^? ^ (7). - ^ A? ^ '(R" 7? ^
Wherein each R7 is independently selected from the group consisting of hydrogen, linear or branched aliphatic hydrocarbon, saturated or unsaturated, substituted or unsubstituted or alkoxy radical having from 1 to 10 carbon atoms, or R7 is a radical alicyclic or aromatic saturated or unsaturated, substituted or unsubstituted having 1 to 10 carbon atoms, which is fused to the heterocyclic ring, each A is independently selected from the group consisting of O and N (R8) a, wherein R8 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon radical having from 1 to 10 carbon atoms, whether or not 0 to 1; z is an integer from 1 to 3. 12. The composition according to any of claims 1-9, further characterized in that R is selected from the group consisting of linear or branched aliphatic hydrocarbon radicals having from 7 to 11 carbon atoms. carbon, x is a number from 6 to 10; and R2 is selected from the group consisting of a hydrocarbon radical of the formula: - C (CH3) 2R3 wherein R3 is selected from the group consisting of linear or branched aliphatic hydrocarbon radicals having from 2 to 5 carbon atoms. 13. The composition according to any of claims 1-8, further characterized in that R2 is a hydrocarbon of the formula: - (CH2) y- X
. . . , ^ L where y is an integer from 0 to 7, and X is a substituted or unsubstituted, saturated or unsaturated cyclic or aromatic hydrocarbon radical of 4 to 8 members.
14. The composition according to any of claims 1-8 and 13, further characterized in that R is selected from the group consisting of linear or branched aliphatic hydrocarbon radicals having from 7 to 11 carbon atoms, x is a number of 6 to 10; and R2 is selected from the group consisting of a hydrocarbon radical of the formula: - < CH2) ^ - X where y is 0 and X is a substituted or unsubstituted, saturated or unsaturated, 5- or 6-membered cyclic or aromatic hydrocarbon radical.
15. The composition according to any of claims 1-8 and 13-14, further characterized in that X is selected from the group consisting of: wherein each R9 is independently selected from the group consisting of hydrogen, aliphatic hydrocarbon radical or straight or branched, saturated or unsaturated, substituted or unsubstituted alkoxy radical of 1 to 10 carbon atoms, or R9 is a saturated alicyclic or aromatic hydrocarbon radical or unsaturated, substituted or unsubstituted having 1 to 10 carbon atoms, which is fused to the ring; w is an integer from 1 to 3.
16. The composition according to any of claims 1-8 and 13-15, further characterized in that X is selected from the group consisting of: where R9 is as defined above.
17. The composition according to any of claims 1-8 and 13-16, further characterized in that X is selected from the group consisting of:
18. - The composition according to any of claims 1, 5 and 6, further characterized in that said composition is in the form of a composition for automatic dishwashing and further comprises 0.01% to 15% of a co-surfactant oxide surfactant. amine.
19. The composition according to any of claims 1-17, further characterized in that said auxiliary ingredient is selected from the group consisting of detergency builders, "",, ...., 1..... . m .. .... - * «.,. .. «-. - * »¿~ ~« «~. dirt-releasing polymers, co-surfactants, polymeric dispersants, polysaccharides, abrasives, bactericides, rust inhibitors, enzymes, dyes, perfumes, thickeners, antioxidants, processing aids, foam enhancers, foam suppressors, pH regulators, agents antifungal or mold control, insect repellents, anticorrosive auxiliaries, chelators, bleaching agents, bleach catalysts and mixtures thereof.
20. The composition according to any of claims 1-19, further characterized in that said composition is in the form of a tablet, granule, powder, liquid, gel, liquid-gel or bar.
21. The composition according to any of claims 4, and 7 to 20, further characterized in that said amine oxide has the formula: wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 1 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
MXPA02005747A 1999-12-08 2000-12-08 Compositions including ether capped poly(oxyalkylated) alcohol surfactants. MXPA02005747A (en)

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