+

WO2000050551A1 - Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes - Google Patents

Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes Download PDF

Info

Publication number
WO2000050551A1
WO2000050551A1 PCT/US2000/003455 US0003455W WO0050551A1 WO 2000050551 A1 WO2000050551 A1 WO 2000050551A1 US 0003455 W US0003455 W US 0003455W WO 0050551 A1 WO0050551 A1 WO 0050551A1
Authority
WO
WIPO (PCT)
Prior art keywords
automatic dishwashing
compositions
mixtures
composition according
nonionic surfactant
Prior art date
Application number
PCT/US2000/003455
Other languages
English (en)
Inventor
Bernard William Kluesener
William Michael Scheper
Mark Robert Sivik
Donna Jean Haeggberg
Glenn Thomas Jordan, Iv
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22394087&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2000050551(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to DE60027549T priority Critical patent/DE60027549T2/de
Priority to AU29900/00A priority patent/AU2990000A/en
Priority to JP2000601115A priority patent/JP2002537484A/ja
Priority to US09/913,870 priority patent/US7012052B1/en
Priority to MXPA01008526A priority patent/MXPA01008526A/es
Priority to CA002369120A priority patent/CA2369120A1/fr
Priority to EP00908588A priority patent/EP1155105B1/fr
Publication of WO2000050551A1 publication Critical patent/WO2000050551A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains

Definitions

  • the present invention is in the field of automatic dishwashing detergents comprising nonionic surfactants and preferably bleach.
  • Automatic dishwashing with bleaching chemicals is different from fabric bleaching.
  • use of bleaching chemicals involves promotion of soil removal from dishes, though soil bleaching may also occur. Additionally, soil antiredeposition and anti-spotting effects from bleaching chemicals are desirable.
  • Some bleaching chemicals (such as a hydrogen peroxide source, alone or together with tetraacetylethylenediamine, aka "TAED") can, in certain circumstances, be helpful for cleaning dishware
  • ADD compositions In spite of such continuing changes to the formulation of ADD compositions, there continues to be a need for better cleaning ADD compositions, especially for elimination of spot filming. Typically, in other types of cleaning compositions such as laundry detergent compositions, cleaning improvements are continually being made by changing and improving the surfactants used. However, as noted hereinbefore, ADD compositions have the unique limitation of requiring very low sudsing compositions which is incompatible with most of the surfactant systems and ingredients typically used in other cleaning compositions. Thus, there continues to be a need for ADD compositions which provide spotting reduction benefits without unacceptably high sudsing.
  • the present invention therefore encompasses automatic dishwashing detergent compositions comprising:
  • R 1 O[CH 2 CH(R 3 )O] e R 2 wherein R ⁇ is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and further optionally substituted with an ether group; R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; e is an integer having an average value from 1 to 40, wherein R 2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; and
  • a bleaching agent preferably a hypochlorite, e.g., sodium dichloroisocyanurate, "NaDCC", or source of hydrogen peroxide bleaching system, e.g. perborate or percarbonate
  • a bleaching agent preferably a hypochlorite, e.g., sodium dichloroisocyanurate, "NaDCC", or source of hydrogen peroxide bleaching system, e.g. perborate or percarbonate
  • a cobalt bleach catalyst and/or a manganese bleach catalyst preferably also containing a cobalt bleach catalyst and/or a manganese bleach catalyst
  • adjunct materials preferably automatic dishwashing detergent adjunct materials selected from the group consisting of enzymes, surfactants other than (b) chelating agents, and mixtures thereof.
  • the present invention encompasses (but is not limited to) granular-form, fully- formulated ADD's in which additional ingredients, including other enzymes (especially proteases and/or amylases) are formulated, along with other ADD product forms such as liquidgels and tablets.
  • additional ingredients including other enzymes (especially proteases and/or amylases) are formulated, along with other ADD product forms such as liquidgels and tablets.
  • the instant invention also encompasses cleaning methods; more particularly, a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising an ADD composition as provided hereinbefore.
  • the invention has advantages, including the excellent greasy soil removal, good dishcare, and good overall cleaning.
  • Automatic dishwashing compositions of the present invention comprise builder and a butoxy capped nonionic surfactant system, and preferably also include a bleaching agent (such as a chlorine bleach or a source of hydrogen peroxide) and/or detersive enzymes.
  • Bleaching agents useful herein include chlorine oxygen bleaches (e.g., hypochlorite or NaDCC) and sources of hydrogen peroxide, including any common hydrogen-peroxide releasing salt, such as sodium perborate, sodium percarbonate, and mixtures thereof. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • additional ingredients such as water-soluble silicates (useful to provide alkalinity and assist in controlling corrosion), dispersant polymers (which modify and inhibit crystal growth of calcium and/or magnesium salts), chelants (which control transition metals), alkalis (to adjust pH), and detersive enzymes (to assist with tough food cleaning, especially of starchy and proteinaceous soils), are present.
  • Additional bleach-modifying materials such as conventional bleach activators (e.g. TAED and/or bleach catalysts) may be added, provided that any such bleach-modifying materials are delivered in such a manner as to be compatible with the purposes of the present invention.
  • the present detergent compositions may, moreover, comprise one or more processing aids, fillers, perfumes, conventional enzyme particle-making materials including enzyme cores or "nonpareils", as well as pigments, and the like.
  • materials used for the production of ADD compositions herein are preferably checked for compatibility with spotting/filming on glassware.
  • Test methods for spotting/filming are generally described in the automatic dishwashing detergent literature, including DIN and ASTM test methods.
  • Certain oily materials, especially at longer chain lengths, and insoluble materials such as clays, as well as long-chain fatty acids or soaps which form soap scum are therefore preferably limited or excluded from the instant compositions.
  • Amounts of the essential ingredients can vary within wide ranges, however preferred automatic dishwashing detergent compositions herein (which typically have a 1% aqueous solution pH of above about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5) are those wherein there is present: from about 5%> to about 90%, preferably from about 5% to about 75%, of builder; from about 0.1% to about 15%>, preferably from about 0.2% to about 10%, of the nonionic surfactant.
  • preferred automatic dishwashing detergent compositions herein which typically have a 1% aqueous solution pH of above about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5 are those wherein there is present: from about 5%> to about 90%, preferably from about 5% to about 75%, of builder; from about 0.1% to about 15%>, preferably from about 0.2% to about 10%, of the nonionic surfactant.
  • Such fully- formulated embodiments typically further comprise from about 0.1% to about 15%) of a polymeric dispersant, from about 0.01%> to about 10% of a chelant, and from about 0.00001%) to about 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
  • a polymeric dispersant from about 0.01%> to about 10% of a chelant, and from about 0.00001%) to about 10% of a detersive enzyme, though further additional or adjunct ingredients may be present.
  • Detergent compositions herein in granular form typically limit water content, for example to less than about 7% free water, for best storage stability.
  • compositions may be formulated using chlorine- containing bleach additive
  • preferred ADD compositions of this invention are substantially free of chlorine bleach.
  • substantially free of chlorine bleach is meant that the formulator does not deliberately add a chlorine-containing bleach additive, such as a dichloroisocyanurate, to the preferred ADD composition.
  • a chlorine-containing bleach additive such as a dichloroisocyanurate
  • the term “substantially free” can be similarly constructed with reference to preferred limitation of other ingredients.
  • the term “effective amount” herein is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance cleaning of a soiled surface.
  • the term “catalytically effective amount” refers to an amount of metal- containing bleach catalyst which is sufficient under whatever comparative test conditions are employed, to enhance cleaning of the soiled surface.
  • the soiled surface may be, for example, a porcelain cup with tea stain, a porcelain cup with lipstick stain, dishes soiled with simple starches or more complex food soils, or a plastic spatula stained with tomato soup.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some machines have considerably longer wash cycles than others.
  • the essential nonionic surfactants of the present invention must have an X/Y number of less than 1.90, preferably less than 1.85, more preferably less than 1.75. The determination of this X/Y number is described hereinafter.
  • the nonionic surfactants of the present invention are selected from the group consisting of:
  • Rl is a linear or branched C6 to C20 alkyl, preferably linear or branched C8 to C18 alkyl, more preferably linear or branched C9 to C16 alkyl;
  • a is an integer from 2 to 30, preferably from 4 to 25, more preferably from 5 to 20 most preferably from 5 to 18;
  • b is an integer from 0 to 30 preferably from 0 to 25, more preferably from 0 to 20, most preferably from 0 to 10;
  • c is an integer from 1 to 30 preferably from 1 to 15, more preferably from 1 to 10, most preferably from 1 to 6;
  • R 1 O[CH 2 CH(R 3 )O] e R 2 wherein R ⁇ is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, optionally containing from 1 to 5 hydroxy groups; and further optionally substituted with an ether group; R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; e is an integer having an average value from 1 to 40, wherein R 2 can optionally be alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures thereof; and (iii) mixtures thereof; Suitable surfactants include, but are not limited to,
  • the LFNI surfactants of the present invention must all have a ratio of hydrophobic to hydrophilic, or "X/Y" number of greater than or equal to 1.00.
  • X/Y is defined as the sum of the protons attached to carbon atoms that are adjacent to oxygen.
  • Y is defined as the sum of all the protons attached to carbon atoms within said molecule that are non-adjacent to oxygen. That is,
  • the "X" protons are represented as the peak area defined by the region of the spectrum from d 3.0 to 4.0 ppm.
  • the "Y” protons are represented as the peak area defined from d 0.5 to 2.0 ppm.
  • X/Y is then calculated by dividing the peak area from 3.0 to 4.0 ppm by the peak area from 0.5 to 2.0 ppm.
  • ADD compositions comprising nonionic surfactant systems wherein the sudsing (absent any silicone suds controlling agent) is less than 2 inches, preferably less than 1 inch, determined as by the method disclosed in US Patent No. 5,294,365.
  • Optional Co-Surfactants may further contain optional co-surfactants. These optional surfactants will be preferably bleach stable. Preferred optional co-surfactants are low cloud point nonionic surfactants, high cloud point nonionic surfactants, anionic surfactants and mixtures thereof.
  • Nonionic co-surfactants useful in the present invention Automatic Dishwashing compositions are when present desirably included in the present detergent compositions at levels of from about 0.1 % to about 15% of the composition.
  • bleach-stable co-surfactants are preferred.
  • Nonionic surfactants generally are well known, being described in more detail in Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems", incorporated by reference 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 is observable is referred to as the “cloud point” (See Kirk Oth er, pp. 360-362, hereinbefore).
  • a "low cloud point" nonionic co-surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30°C, preferably less than about 20°C, and most preferably less than about 10°C.
  • Typical low cloud point nonionic co-surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • low cloud point nonionic co-surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly- Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation).
  • ethoxylated-propoxylated alcohol e.g., Olin Corporation's Poly- Tergent® SLF18
  • epoxy-capped poly(oxyalkylated) alcohols e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.
  • Nonionic co-surfactants can optionally contain propylene oxide in an amount up to about 15%) by weight.
  • Other preferred nonionic co-surfactants can be prepared by the processes described in U.S. Patent 4,223,163, issued September 16, 1980, Builloty, incorporated herein by reference.
  • Low cloud point nonionic co-surfactants additionally comprise a polyoxyethylene, polyoxypropylene block polymeric compound.
  • Block polyoxyethylene- polyoxypropylene polymeric compounds include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound.
  • block polymer surfactant compounds designated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.
  • Preferred examples include REVERSED PLURONIC® 25R2 and TETRONIC® 702, Such co-surfactants are typically useful herein as low cloud point nonionic surfactants.
  • a "high cloud point" nonionic co-surfactant is defined as a nonionic surfactant system ingredient having a cloud point of greater than 40°C, preferably greater than about 50°C, and more preferably greater than about 60°C.
  • the nonionic co-surfactant system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, with from about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
  • Such high cloud point nonionic co-surfactants include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • the high cloud point nonionic co-surfactant further have a hydrophile-lipophile balance ("HLB"; see Kirk Othmer hereinbefore) value within the range of from about 9 to about 15, preferably 11 to 15.
  • HLB hydrophile-lipophile balance
  • Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
  • high cloud point nonionic co-surfactant is derived from a straight or preferably branched chain or secondary fatty alcohol containing from about 6 to about 20 carbon atoms (Cg-C20 alcohol), including secondary alcohols and branched chain primary alcohols.
  • high cloud point nonionic co-surfactants are branched or secondary alcohol ethoxylates, more preferably mixed C9/11 or Cl l/15 branched alcohol ethoxylates, condensed with an average of from about 6 to about 15 moles, preferably from about 6 to about 12 moles, and most preferably from about 6 to about 9 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated nonionic co-surfactant so derived has a narrow ethoxylate distribution relative to the average.
  • the optional co-surfactants are a mixture of low cloud point nonionics and high cloud point nonionics it is preferred that the mixture is combined in a weight ratio preferably within the range of from about 10:1 to about 1 :10.
  • the anionic co-surfactant may be selected from alkylethoxycarboxylates, alkyl ethoxysulfates, with the degree of ethoxylation greater than 3 (preferably 4 to 10; more preferably 6 to 8), and chain length in the range of C8 to C16, preferrably 11-15.
  • branched alkylcarboxylates have been found to be useful in ADW compositions when the branch occurs in the middle and the average total chain length is 10 to 18, preferably 12-16 with the side branch 2-4 carbons in length.
  • An example is 2- butyloctanoic acid.
  • the anionic co-surfactant is typically of a type having good solubility in the presence of calcium.
  • Such anionic co-surfactants are further illustrated by alkyl(polyethoxy)sulfates (AES), alkyl (polyethoxy)carboxylates (AEC), and short chained Cg-Cio alkyl sulfates and sulfonates. Straight chain fatty acids have been shown to be ineffective due to their sensitivity to calcium.
  • Detergent builders other than silicates can optionally be included in the compositions herein to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are used in automatic dishwashing to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1%> builder.
  • High performance compositions typically comprise from about 5% to about 90%), more typically from about 5% to about 75% by weight, of the detergent builder. Lower or higher levels of builder, however, are not excluded.
  • Inorganic or non-phosphate-containing detergent builders include, but are not limited to, phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, citrate, zeolite or layered silicate, and aluminosilicates.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • Various grades and types of sodium carbonate and sodium sesquicarbonate may be used, certain of which are particularly useful as carriers for other ingredients, especially detersive surfactants.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt or "overbased". When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty laundry detergent and automatic dishwashing formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in combination with zeolite, the aforementioned BRITESIL types, and/or layered silicate builders. Oxydisuccinates are also useful in such compositions and combinations.
  • succinic acid builders include the C5- C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Fatty acids e.g., Ci 2-C ⁇ g monocarboxylic acids
  • Ci 2-C ⁇ g monocarboxylic acids may also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity but are generally not desired.
  • Such use of fatty acids will generally result in a diminution of sudsing in laundry compositions, which may need to be be taken into account by the formulator.
  • Fatty acids or their salts are undesirable in Automatic Dishwashing (ADD) embodiments in situations wherein soap scums can form and be deposited on dishware.
  • ADD Automatic Dishwashing
  • phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- 1 - hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used though such materials are more commonly used in a low-level mode as chelants or stabilizers.
  • Phosphate detergent builders for use in ADD compositions are well known. They include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Phosphate builder sources are described in detail in Kirk Othmer, 3rd Edition, Vol. 17, pp. 426-472 and in "Advanced Inorganic Chemistry” by Cotton and Wilkinson, pp. 394-400 (John Wiley and Sons, Inc.; 1972).
  • Preferred levels of phosphate builders herein are from about 10%> to about 75%, preferably from about 15%> to about 50%, of phosphate builder.
  • Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.
  • An "effective amount" of a source of hydrogen peroxide is any amount capable of measurably improving stain removal (especially of tea stains) from soiled dishware compared to a hydrogen peroxide source-free composition when the soiled dishware is washed by the consumer in a domestic automatic dishwasher in the presence of alkali.
  • a source of hydrogen peroxide herein is any convenient compound or mixture which under consumer use conditions provides an effective amount of hydrogen peroxide. Levels may vary widely and are usually in the range from about 0.1%) to about 70%, more typically from about 0.5%> to about 30%o, by weight of the ADD compositions herein.
  • the preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself.
  • perborate e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide
  • sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont).
  • Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10%> by weight of said particles being smaller than about 200 micrometers and not more than about 10%> by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with a silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material.
  • a chlorine-type bleaching material include for example sodium dichloroisocyanurate (“NaDCC").
  • ADD compositions herein may comprise only the nonionic surfactant system and builder
  • fully-formulated ADD compositions typically will also comprise other automatic dishwashing detergent adjunct materials to improve or modify performance. These materials are selected as appropriate for the properties required of an automatic dishwashing composition.
  • low spotting and filming is desired
  • preferred compositions have spotting and filming grades of 3 or less, preferably less than 2, and most preferably less than 1, as measured by the standard test of The American Society for Testing and Materials ("ASTM”) D3556-85 (Reapproved 1989) "Standard Test Method for Deposition on Glassware During Mechanical Dishwashing".
  • Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. They are further selected based on the form of the composition, i.e., whether the composition is to be sold as a liquid, paste (semi-solid), or solid form (including tablets and the preferred granular forms for the present compositions).
  • adjunct materials which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct materials comprise, in total, from about 30% to about 99.9%, preferably from about 70%> to about 95%>, by weight of the compositions), include other active ingredients such as non-phosphate builders, chelants, enzymes, suds suppressors, dispersant polymers (e.g., from BASF Corp.
  • Detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance benefits.
  • “Detersive enzyme”, as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in an ADD composition.
  • Such detersive enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase. Enzymes when present in the compositions, at from about 0.0001%> to about 5%> of active enzyme by weight of the detergent composition. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more bleach compatible, have a remaining degree of bleach deactivation susceptibility.
  • proteolytic Enzyme can be of animal, vegetable or microorganism (preferred) origin.
  • the proteases for use in the detergent compositions herein include (but are not limited to) trypsin, subtilisin, chymotrypsin and elastase-type proteases.
  • Preferred for use herein are subtilisin-type proteolytic enzymes.
  • Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus subtilis and/or Bacillus licheniformis.
  • Suitable proteolytic enzymes include Novo Industri A/S Alcalase® (preferred), Esperase®' Savinase® (Copenhagen, Denmark), Gist-brocades' Maxatase®, Maxacal® and Maxapem 15® (protein engineered Maxacal®) (Delft, Netherlands), and subtilisin BPN and BPN'(preferred), which are commercially available.
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those made by Genencor International, Inc. (San Francisco, California) which are described in European Patent 251,446B, granted December 28, 1994 (particularly pages 17, 24 and 98) and which are also called herein "Protease B".
  • Protease A a modified bacterial serine proteolytic enzyme
  • BPN' modified bacterial serine proteolytic enzyme
  • Preferred proteolytic enzymes are selected from the group consisting of Alcalase ® (Novo Industri A/S), BPN', Protease A and Protease B (Genencor), and mixtures thereof. Protease B is most preferred.
  • proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention.
  • 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 for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, 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 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International (A. Baeck et al. entitled "Protease-Containing Cleaning Composition
  • proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Amylase - Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate- based stains.
  • Suitable amylases are Termamyl® (Novo Nordisk), Fungamyl® and BAN® (Novo Nordisk).
  • the enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Amylase enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2%>, preferably from about 0.0001% to about 0.5%), more preferably from about 0.0005%> to about 0.1 %>, even more preferably from about 0.001% to about 0.05% of active enzyme by weight of the detergent composition.
  • Amylase enzymes also include those described in WO95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056.
  • One suitable amylase enzyme is NATALASE® available from Novo Nordisk.
  • amylases suitable herein include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful.
  • amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®.
  • Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
  • carbohydrase enzymes which impart antimicrobial activity may also be included in the present invention.
  • Such enzymes include endoglycosidase, Type II endoglycosidase and glucosidase as disclosed in U.S. Patent Nos. 5,041,236, 5,395,541, 5,238,843 and 5,356,803 the disclosures of which are herein incorporated by reference.
  • other enzymes having antimicrobial activity may be employed as well including peroxidases, oxidases and various other enzymes.
  • compositions of the present invention when any enzyme is present in the composition.
  • Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • the present invention encompasses peroxidase-free automatic dishwashing composition embodiments.
  • the peroxygen bleach component in the composition is formulated with an activator (peracid precursor).
  • the activator is present at levels of from about 0.01%) to about 15%, preferably from about 0.5% to about 10%>, more preferably from about 1%) to about 8%, by weight of the composition.
  • Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (CJO-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam.
  • Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
  • Preferred bleach activators are those described in U.S. Patent 5,130,045, Mitchell et al, and 4,412,934, Chung et al, and copending patent applications U. S. Serial Nos. 08/064,624, 08/064,623, 08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending application to M. Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. 08/133,691 (P&G Case 4890R), all of which are incorporated herein by reference.
  • the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 :1, preferably from about 20:1 to about 1:1, more preferably from about 10:1 to about 3:1.
  • Quaternary substituted bleach activators may also be included.
  • the present detergent compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former.
  • QSBA quaternary substituted bleach activator
  • QSP quaternary substituted peracid
  • compositions and methods utilize metal-containing bleach catalysts that are effective for use in ADD compositions.
  • Preferred are manganese and cobalt-containing bleach catalysts.
  • cobalt pentaamine chloride salts having the formula [Co(NH3)5Cl] Yy, and especially [Co(NH3)5Cl]Cl2-
  • cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH 3 ) 5 OAc](OAc)2; [Co(NH 3 ) 5 OAc](PF 6 )2; [Co(NH 3 ) 5 OAc](SO4) ; [Co- (NH 3 ) 5 OAc](BF 4 )2; and [Co(NH 3 ) 5 OAc](NO 3 )2.
  • the cleaning compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor.
  • typical automatic dishwashing compositions herein will comprise from about 0.0005%> to about 0.2%, more preferably from about 0.004% to about 0.08%>, of bleach catalyst by weight of the cleaning compositions. 4.
  • compositions herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art.
  • the preferred ADD compositions herein comprise a pH-adjusting component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders.
  • the pH-adjusting components are selected so that when the ADD is dissolved in water at a concentration of 1,000 - 10,000 ppm, the pH remains in the range of above about 8, preferably from about 9.5 to about 11.
  • the preferred nonphosphate pH-adjusting component of the invention is selected from the group consisting of: (i) sodium carbonate or sesquicarbonate; (ii) sodium silicate, preferably hydrous sodium silicate having SiO2:Na2O ratio of from about 1 :1 to about 2:1, and mixtures thereof with limited quantites of sodium metasilicate; (iii) sodium citrate; (iv) citric acid; (v) sodium bicarbonate; (vi) sodium borate, preferably borax; (vii) sodium hydroxide; and (viii) mixtures of (i)-(vii).
  • Preferred embodiments contain low levels of silicate (i.e. from about 3% to about 10% SiO 2 ).
  • Illustrative of highly preferred pH-adjusting component systems are binary mixtures of granular sodium citrate with anhydrous sodium carbonate, and three- component mixtures of granular sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate.
  • the amount of the pH adjusting component in the instant ADD compositions is preferably from about 1%> to about 50%, by weight of the composition.
  • the pH-adjusting component is present in the ADD composition in an amount from about 5% to about 40%, preferably from about 10%> to about 30%, by weight.
  • compositions herein having a pH between about 9.5 and about 11 of the initial wash solution particularly preferred ADD embodiments comprise, by weight of ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most preferably from about 15%> to about 20%, of sodium citrate with from about 5% to about 30%>, preferably from about 7% to 25%, most preferably from about 8%> to about 20%> sodium carbonate.
  • the essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from nonphosphate detergency builders known in the art, which include the various water- soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid; nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
  • the present automatic dishwashing detergent compositions may further comprise water-soluble silicates.
  • Water-soluble silicates herein are any silicates which are soluble to the extent that they do not adversely affect spotting/filming characteristics of the ADD composition.
  • silicates are sodium metasilicate and, more generally, the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1; and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6® is a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6"
  • Na SKS-6 and other water-soluble silicates usefule herein do not contain aluminum.
  • NaSKS-6 is the ⁇ -Na2Si ⁇ 5 form of layered silicate and can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043.
  • SKS-6 is a preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ +i-yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ -, ⁇ - and ⁇ - forms.
  • Other silicates may also be useful, such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. 21
  • Silicates particularly useful in automatic dishwashing (ADD) applications include granular hydrous 2-ratio silicates such as BRITESIL® H20 from PQ Corp., and the commonly sourced BRITESIL® H24 though liquid grades of various silicates can be used when the ADD composition has liquid form.
  • BRITESIL® H20 from PQ Corp.
  • BRITESIL® H24 liquid grades of various silicates can be used when the ADD composition has liquid form.
  • sodium metasilicate or sodium hydroxide alone or in combination with other silicates may be used in an ADD context to boost wash pH to a desired level.
  • compositions herein may also optionally contain one or more transition-metal selective sequestrants, "chelants” or “chelating agents”, e.g., iron and/or copper and/or manganese chelating agents.
  • Chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, phosphonates (especially the aminophosphonates), polyfunctionally-substituted aromatic chelating agents, and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to control iron, copper and manganese in washing solutions which are known to decompose hydrogen peroxide and/or bleach activators; other benefits include inorganic film prevention or scale inhibition.
  • Commercial chelating agents for use herein include the DEQUEST® series, and chelants from Monsanto, DuPont, and Nalco, Inc.
  • Aminocarboxylates useful as optional chelating agents are further illustrated by ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof.
  • chelant mixtures may be used for a combination of functions, such as multiple transition-metal control, long-term product stabilization, and/or control of precipitated transition metal oxides and/or hydroxides.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3,5-disulfobenzene.
  • a highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • EDDS ethylenediamine disuccinate
  • the trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.
  • Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are acceptable in detergent compositions, and include the ethylenediaminetetrakis (methylenephosphonates) and the diethylenetriaminepentakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Dispersant Polymer - Preferred ADD compositions herein may additionally contain a dispersant polymer.
  • a dispersant polymer in the instant ADD compositions is typically at levels in the range from 0 to about 25%>, preferably from about 0.5% to about 20%, more preferably from about 1% to about 8%> by weight of the ADD composition.
  • Dispersant polymers are useful for improved filming performance of the present ADD compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
  • Dispersant polymers suitable for use herein are further illustrated by the film- forming polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983.
  • Suitable polymers are preferably at least partially neutralized or alkali metal, ammonium or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of polycarboxylic acids.
  • the alkali metal, especially sodium salts are most preferred.
  • the molecular weight of the polymer can vary over a wide range, it preferably is from about 1,000 to about 500,000, more preferably is from about 1,000 to about 250,000, and most preferably, especially if the ADD is for use in North American automatic dishwashing appliances, is from about 1,000 to about 5,000.
  • suitable dispersant polymers include those disclosed in U.S. Patent No. 3,308,067 issued March 7, 1967, to Diehl.
  • Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • monomeric segments containing no carboxylate radicals such as methyl vinyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 50% by weight of the dispersant polymer.
  • Copolymers of acrylamide and acrylate 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. Most preferably, such dispersant polymer has a molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer.
  • Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers.
  • Such copolymers contain as monomer units: a) from about 90%) to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula: - [(C(R2)C(Rl)(C(O)OR 3 )] wherein the apparently unfilled valencies are in fact occupied by hydrogen and at least one of the substituents Rl, R 2 , or R 3 , preferably R!
  • R 2 is a 1 to 4 carbon alkyl or hydroxyalkyl group; R ⁇ or R 2 can be a hydrogen and R 3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein Rl is methyl, R 2 is hydrogen, and R 3 is sodium.
  • Suitable low molecular weight polyacrylate dispersant 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 herein has a molecular weight of about 3,500 and is the fully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30%) by weight methacrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,766, and 5,084,535.
  • Agglomerated forms of the present ADD compositions may employ aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • aqueous solutions of polymer dispersants as liquid binders for making the agglomerate (particularly when the composition consists of a mixture of sodium citrate and sodium carbonate).
  • polyacrylates with an average molecular weight of from about 1 ,000 to about 10,000
  • acrylate/maleate or acrylate/fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 1:2.
  • Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982.
  • dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds for example, having a melting point within the range of from about 30°C to about 100°C, can be obtained at molecular weights of 1,450, 3,400, 4,500, 6,000, 7,400, 9,500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol.
  • the polyethylene, polypropylene and mixed glycols are referred to using the formula:
  • dispersant polymers useful herein include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose sulfate.
  • Sodium cellulose sulfate is the most preferred polymer of this group.
  • Suitable dispersant polymers are the carboxylated polysaccharides, particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, 1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described in U.S. Pat. No. 4,141,841, McDonald, issued Feb. 27, 1979.
  • Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses.
  • organic dispersant polymers such as polyaspartate.
  • the present ADD compositions may contain one or more material care agents which are effective as corrosion inhibitors and/or anti-tarnish aids.
  • material care agents are preferred components of machine dishwashing compositions especially in certain European countries where the use of electroplated nickel silver and sterling silver is still comparatively common in domestic flatware, or when aluminium protection is a concern and the composition is low in silicate.
  • material care agents include metasilicate, silicate, bismuth salts, manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and mixtures thereof.
  • 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 ratio of cyclic to noncyclic hydrocarbons of about 32:68.
  • a paraffin oil meeting those characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
  • the addition of low levels of bismuth nitrate i.e., Bi(NO3)3 is also preferred.
  • corrosion inhibitor compounds include benzotriazole and comparable compounds; mercaptans or thiols including thionaphtol and thioanthranol; and finely divided Aluminium fatty acid salts, such as aluminium tristearate.
  • the formulator will recognize that such materials will generally be used judiciously and in limited quantities so as to avoid any tendency to produce spots or films on glassware or to compromise the bleaching action of the compositions. For this reason, mercaptan anti-tarnishes which are quite strongly bleach-reactive and common fatty carboxylic acids which precipitate with calcium in particular are preferably avoided.
  • the ADD's of the invention can optionally contain an alkyl phosphate ester suds suppressor, a silicone suds suppressor, or combinations thereof. Levels in general are from 0% to about 10%>, preferably, from about 0.001%) to about 5%>. However, generally (for cost and/or deposition considerations) preferred compositions herein do not comprise suds suppressors or comprise suds suppressors only at low levels, e.g., less than about 0.1 %> of active suds suppressing agent.
  • Silicone suds suppressor technology and other defoaming agents useful herein are extensively documented in "Defoaming, Theory and Industrial Applications", Ed., P.R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6, incorporated herein by reference. See especially the chapters entitled “Foam control in Detergent Products” (Ferch et al) and “Surfactant Antifoams” (Blease et al). See also U.S. Patents 3,933,672 and 4,136,045.
  • Highly preferred silicone suds suppressors are the compounded types known for use in laundry detergents such as heavy-duty granules, although types hitherto used only in heavy-duty liquid detergents may also be incorporated in the instant compositions.
  • polydimethylsiloxanes having trimethylsilyl or alternate endblocking units may be used as the silicone.
  • These may be compounded with silica and/or with surface-active nonsilicon components, as illustrated by a suds suppressor comprising 12%> silicone/silica, 18% stearyl alcohol and 70% starch in granular form.
  • a suitable commercial source of the silicone active compounds is Dow Corning Corp.
  • a phosphate ester suitable compounds are disclosed in U.S. Patent 3,314,891, issued April 18, 1967, to Schmolka et al, incorporated herein by reference.
  • Preferred alkyl phosphate esters contain from 16-20 carbon atoms.
  • Highly preferred alkyl phosphate esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts thereof, particularly alkali metal salts, or mixtures thereof.
  • filler materials can also be present in the instant ADDs. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate, etc., in amounts up to about 70%), preferably from 0%> to about 40%> of the ADD composition.
  • Preferred filler is sodium sulfate, especially in good grades having at most low levels of trace impurities.
  • Sodium sulfate used herein preferably has a purity sufficient to ensure it is non- reactive with bleach; it may also be treated with low levels of sequestrants, such as phosphonates or EDDS in magnesium-salt form. Note that preferences, in terms of purity sufficient to avoid decomposing bleach, applies also to pH-adjusting component ingredients, specifically including any silicates used herein.
  • the present invention encompasses embodiments which are substantially free from sodium chloride or potassium chloride.
  • Hydrotrope materials such as sodium benzene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, etc., can be present, e.g., for better dispersing surfactant.
  • Bleach-stable perfumes (stable as to odor); and bleach-stable dyes such as those disclosed in U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987 can also be added to the present compositions in appropriate amounts.
  • Other common detergent ingredients consistent with the spirit and scope of the present invention are not excluded.
  • ADD compositions herein can contain water-sensitive ingredients or ingredients which can co-react when brought together in an aqueous environment, it is desirable to keep the free moisture content of the ADDs at a minimum, e.g., 7% or less, preferably 4% or less of the ADD; and to provide packaging which is substantially impermeable to water and carbon dioxide. Coating measures have been described herein to illustrate a way to protect the ingredients from each other and from air and moisture. Plastic bottles, including refillable or recyclable types, as well as conventional barrier cartons or boxes are another helpful means of assuring maximum shelf-storage stability. As noted, when ingredients are not highly compatible, it may further be desirable to coat at least one such ingredient with a low-foaming nonionic surfactant for protection. There are numerous waxy materials which can readily be used to form suitable coated particles of any such otherwise incompatible components; however, the formulator prefers those materials which do not have a marked tendency to deposit or form films on dishes including those of plastic construction.
  • Some preferred substantially chlorine bleach-free granular automatic dishwashing compositions of the invention are as follows: a substantially chlorine-bleach free automatic dishwashing composition comprising amylase (e.g., TERMAMYL®) and/or a bleach stable amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate and a cobalt catalyst as defined herein.
  • a substantially chlorine-bleach free automatic dishwashing composition comprising an oxidative stability-enhanced amylase and a bleach system comprising a source of hydrogen peroxide selected from sodium perborate and sodium percarbonate, a cobalt catalyst, and TAED or NOBS.
  • the present invention also encompasses a method for cleaning soiled tableware comprising contacting said tableware with an aqueous medium comprising a cobalt catalyst, preferably at a concentration of from about 2 ppm to about 10 ppm, as described herein before.
  • Preferred aqueous medium have an initial pH in a wash solution of above about 8, more preferably from about 9.5 to about 12, most preferably from about 9.5 to about 10.5.
  • This invention also encompasses a method of washing tableware in a domestic automatic dishwashing appliance, comprising treating the soiled tableware in an automatic dishwasher with an aqueous alkaline bath comprising the ADW composition of the present invention.
  • Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round- bottomed flask, fitted with a heating mantle, magnetic stirrer, pressure equalizing dropping funnel, reflux condenser, internal thermometer and argon inlet, and dried under vacuum at 75 °C. After releasing the vacuum with argon, sodium metal (0.03 g, 1.2 mmol) is placed into the flask and the mixture heated and stirred at 140 °C until all sodium is consumed. 1,2-Epoxybutane (12.71 g, 176.2 mmol) is then added dropwise at a rate so as to keep the reaction temperature at >120 °C, with a target of 140 °C.
  • Neodol 91-8 (30.00 g, 58.7 mmol) is placed into a 250 ml three-necked round- bottomed flask, fitted with a heating mantle, magnetic stirrer, internal thermometer and argon inlet, and dried under vacuum at 75°C. After cooling to ambient and releasing the vacuum with argon, methylene chloride (12ml) and 2-methyl-l-butene (4.53 g, 64.6 mmol) are added. Then boron trifluoride diethyl etherate (0.83 g, 5.9 mmol) is added all at once.
  • Anhydrous tetrahydrofuran (250 ml) and 60% sodium hydride (8.22 g, 205.6 mmol) are placed into a 500 ml three-necked round-bottomed flask, fitted with a magnetic stirrer, pressure equalizing dropping funnel, internal thermometer and argon inlet. After cooling the mixture to 0 °C, Neodol 91-8 (35.00 g, 68.5 mmol) is added dropwise over 10 minutes. After warming to ambient, the mixture is stirred for 2 h. 1- Iodopentane (33.93 g, 171.3 mmol) is added dropwise over 10 minutes.
  • compositions suitable for use in methods of the present invention are illustrated.
  • Nonionic Surfactant 1 3.0 3.0
  • Amylase (0.8% active) 0.5 0.5
  • Nonionic surfactant according to Example 1.
  • Pentaamineacetatocobalt(i ⁇ ) nitrate prepared as described hereinbefore; may be replaced by MnTacN.
  • compositions which contain a bleach/enzyme particle, but are not intended to be limiting thereof. These compositions are suitable for use in the methods of the present invenetion. All percentages noted are by weight of the finished compositions, other than the perborate (monohydrate) component, which is listed as AvO.
  • Nonionic Surfactant 3 2.0 2.0 ⁇ nHnim ⁇ l ⁇ t Rsl nnr-p
  • Pentaamineacetatocobalt( ⁇ i) nitrate may be replaced by MnTacN.
  • the catalyst and enzymes are introduced into the compositions as 200-2400 micron composite particles which are prepared by spray coating, fluidized bed granulation, marumarizing, prilling, or flaking/grinding operations.
  • the protease and amylase enzymes may be separately formed into their respective catalyst/enzyme composite particles, for reasons of stability, and these separate compositions added to the compositions.
  • Nonionic Surfactant 3 15.0 8.0
  • Nonionic Surfactant 3 3.0 3.0 Ral ⁇ nrp
  • Pentaamineacetatocobalt(III) nitrate may be replaced by MnTacN

Landscapes

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

Abstract

L'invention porte sur des compositions détergentes pour lave-vaisselle comportant: a) 5 % à 90 % en poids de renforçateur; b) 0,1 % à 15 % en poids de: i) un surfactant de formule R1(EO)a(PO)b(BO)c, où R1 est un alkyle C¿6? à C20 linéaire ou ramifié; a est de 2 à 30; b est de 0 à 30; c est de 1 à 30; et ledit surfactant présente un indice X/Y inférieur à 1,90; ou bien ii) un surfactant de formule R?1O[CH¿2CH(R3)O]eR?2, où R1¿ est un radical hydrocarbure présentant de 1 à 30 atomes de carbone; R2 est un radical hydrocarbure présentant de 1 à 30 atomes de carbone; R3 est H, ou un radical aliphatique linéaire d'hydrocarbure présentant de 1 à 4 atomes de carbone; e est un entier d'une valeur moyenne de 1 à 40; c) facultativement de 0,1 % à 40 % en poids d'un agent de blanchiment; et d) des additifs tels que des enzymes, des surfactants autres que (b), ou des chélateurs.
PCT/US2000/003455 1999-02-22 2000-02-10 Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes WO2000050551A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE60027549T DE60027549T2 (de) 1999-02-22 2000-02-10 Maschinengeschirrspülmittel enthaltend ausgewählte nichtionische tenside
AU29900/00A AU2990000A (en) 1999-02-22 2000-02-10 Automatic dishwashing compositions comprising selected nonionic surfactants
JP2000601115A JP2002537484A (ja) 1999-02-22 2000-02-10 選択した非イオン性界面活性剤を含有する自動食器洗浄用組成物
US09/913,870 US7012052B1 (en) 1999-02-22 2000-02-10 Automatic dishwashing compositions comprising selected nonionic surfactants
MXPA01008526A MXPA01008526A (es) 1999-02-22 2000-02-10 Composiciones para el lavado automatico de vajillas que comprenden agentes tensioactivos no ionicos seleccionados.
CA002369120A CA2369120A1 (fr) 1999-02-22 2000-02-10 Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes
EP00908588A EP1155105B1 (fr) 1999-02-22 2000-02-10 Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12103499P 1999-02-22 1999-02-22
US60/121,034 1999-02-22

Publications (1)

Publication Number Publication Date
WO2000050551A1 true WO2000050551A1 (fr) 2000-08-31

Family

ID=22394087

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/003455 WO2000050551A1 (fr) 1999-02-22 2000-02-10 Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes

Country Status (8)

Country Link
EP (1) EP1155105B1 (fr)
JP (1) JP2002537484A (fr)
AT (1) ATE324426T1 (fr)
AU (1) AU2990000A (fr)
CA (1) CA2369120A1 (fr)
DE (1) DE60027549T2 (fr)
MX (1) MXPA01008526A (fr)
WO (1) WO2000050551A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
WO2007004175A1 (fr) * 2005-06-30 2007-01-11 The Procter & Gamble Company Composition detergente pour lave-vaisselle automatique contenant une teneur limitee en phosphates
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
DE102007019458A1 (de) 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
WO2009155187A1 (fr) * 2008-06-18 2009-12-23 Dow Global Technologies Inc. Compositions de nettoyage contenant des alcoolates de gamme moyenne
WO2012123452A1 (fr) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Détergents pour vaisselle
WO2014047934A1 (fr) * 2012-09-29 2014-04-03 Dow Global Technologies Llc Compositions d'alcoxylates et leur utilisation comme adjuvants agricoles
WO2017218222A1 (fr) * 2016-06-16 2017-12-21 Dow Global Technologies Llc Composition pour lave-vaisselle présentant un tensioactif de prévention de taches
US10696925B2 (en) * 2017-03-30 2020-06-30 Dow Global Technologies Llc Automatic dishwashing compositions with dispersant blend

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5213091B2 (ja) * 2006-08-22 2013-06-19 ディバーシー株式会社 自動食器洗浄機用粒状洗浄剤組成物およびその製法、並びにその使用方法
EP3998328A1 (fr) * 2009-02-09 2022-05-18 The Procter & Gamble Company Composition de détergent
GB0917740D0 (en) * 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
US9096818B2 (en) * 2011-12-09 2015-08-04 Clariant International Ltd. Automatic dishwashing detergent compositions comprising ethercarboxylic acids or their salts and nonionic surfactants with a high cloud point
EP2890771A1 (fr) 2012-08-28 2015-07-08 Henkel AG&Co. KGAA Produit pour laver la vaisselle contenant un alkyléthersulfate
JP5801941B1 (ja) * 2014-11-21 2015-10-28 株式会社ニイタカ 洗浄剤組成物、食器洗浄方法、液体洗浄剤組成物用キット及びカートリッジ洗浄剤

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054895A1 (fr) * 1980-12-23 1982-06-30 Hoechst Aktiengesellschaft Mélange d'agents surfactifs pour le nettoyage de surfaces dures
EP0124815A2 (fr) * 1983-05-02 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Utilisation d'éthers de polyglycol comme additifs supprimant la mousse dans des agents de nettoyage peu écumants
GB2158080A (en) * 1984-03-02 1985-11-06 Abm Chemicals Ltd End-blocked nonionic surfactants
EP0254208A2 (fr) * 1986-07-24 1988-01-27 Henkel Kommanditgesellschaft auf Aktien Mélanges d'agents tensio-actifs peu moussants et/ou anti-mousse et leur utilisation
EP0343504A1 (fr) * 1988-05-27 1989-11-29 Henkel Kommanditgesellschaft auf Aktien Ethers de polyglycol supprimant la mousse pour des produits de nettoyage
WO1995034633A1 (fr) * 1994-06-14 1995-12-21 Ecolab Inc. Detergent moule a efficacite amelioree
WO1998011186A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions pour lave-vaisselle, contenant des tensioactifs non ioniques faiblement moussants et agissant en conjonction avec des enzymes
WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0054895A1 (fr) * 1980-12-23 1982-06-30 Hoechst Aktiengesellschaft Mélange d'agents surfactifs pour le nettoyage de surfaces dures
EP0124815A2 (fr) * 1983-05-02 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Utilisation d'éthers de polyglycol comme additifs supprimant la mousse dans des agents de nettoyage peu écumants
GB2158080A (en) * 1984-03-02 1985-11-06 Abm Chemicals Ltd End-blocked nonionic surfactants
EP0254208A2 (fr) * 1986-07-24 1988-01-27 Henkel Kommanditgesellschaft auf Aktien Mélanges d'agents tensio-actifs peu moussants et/ou anti-mousse et leur utilisation
EP0343504A1 (fr) * 1988-05-27 1989-11-29 Henkel Kommanditgesellschaft auf Aktien Ethers de polyglycol supprimant la mousse pour des produits de nettoyage
WO1995034633A1 (fr) * 1994-06-14 1995-12-21 Ecolab Inc. Detergent moule a efficacite amelioree
WO1998011186A1 (fr) * 1996-09-11 1998-03-19 The Procter & Gamble Company Compositions pour lave-vaisselle, contenant des tensioactifs non ioniques faiblement moussants et agissant en conjonction avec des enzymes
WO1999006466A1 (fr) * 1997-08-02 1999-02-11 The Procter & Gamble Company Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365785B1 (en) * 1997-08-02 2002-04-02 Therprocter & Gamble Company Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants
EP3450533A1 (fr) * 2005-06-30 2019-03-06 The Procter & Gamble Company Composition détergente pour lave-vaisselle automatique contenant une teneur limitée en phosphates
WO2007004175A1 (fr) * 2005-06-30 2007-01-11 The Procter & Gamble Company Composition detergente pour lave-vaisselle automatique contenant une teneur limitee en phosphates
EP2520641A1 (fr) * 2005-06-30 2012-11-07 The Procter & Gamble Company Composition détergente pour lave-vaisselle automatique contenant une teneur limitée en phosphates
DE102007019458A1 (de) 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
US8123867B2 (en) 2007-04-25 2012-02-28 Basf Se Phosphate-free dishwasher detergent with excellent rinsing power
US8152931B2 (en) 2007-04-25 2012-04-10 Basf Se Dishwasher detergent with excellent rinsing power
DE102007019457A1 (de) 2007-04-25 2008-10-30 Basf Se Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
WO2009155187A1 (fr) * 2008-06-18 2009-12-23 Dow Global Technologies Inc. Compositions de nettoyage contenant des alcoolates de gamme moyenne
WO2012123452A1 (fr) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Détergents pour vaisselle
EP2877563A4 (fr) * 2012-09-29 2016-01-13 Dow Global Technologies Llc Compositions d'alcoxylates et leur utilisation comme adjuvants agricoles
WO2014047934A1 (fr) * 2012-09-29 2014-04-03 Dow Global Technologies Llc Compositions d'alcoxylates et leur utilisation comme adjuvants agricoles
WO2017218222A1 (fr) * 2016-06-16 2017-12-21 Dow Global Technologies Llc Composition pour lave-vaisselle présentant un tensioactif de prévention de taches
CN109477040A (zh) * 2016-06-16 2019-03-15 陶氏环球技术有限责任公司 具有防斑表面活性剂的自动餐具洗涤组合物
US20190218477A1 (en) * 2016-06-16 2019-07-18 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant
US10774291B2 (en) 2016-06-16 2020-09-15 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant
AU2017286154B2 (en) * 2016-06-16 2021-04-01 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant
US10696925B2 (en) * 2017-03-30 2020-06-30 Dow Global Technologies Llc Automatic dishwashing compositions with dispersant blend

Also Published As

Publication number Publication date
ATE324426T1 (de) 2006-05-15
CA2369120A1 (fr) 2000-08-31
DE60027549D1 (de) 2006-06-01
JP2002537484A (ja) 2002-11-05
EP1155105A1 (fr) 2001-11-21
EP1155105B1 (fr) 2006-04-26
MXPA01008526A (es) 2002-06-04
DE60027549T2 (de) 2007-04-26
AU2990000A (en) 2000-09-14

Similar Documents

Publication Publication Date Title
EP0874895B1 (fr) Compositions pour lave-vaisselle a base de phosphates et de catalyseurs
EP0927237B1 (fr) Compositions peu moussantes pour lave-vaisselle automatiques
EP0807160B1 (fr) Methode pour laver automatiqement la vaisselle maculee de tache de the, o une composition comprenant des catalyseurs cobalt (iii) est utilisee
US5804542A (en) Automatic dishwashing compositions comprising cobalt catalysts
EP0807159B1 (fr) Compositions pour lave-vaisselles automatiques comprenant des catalyseurs chelates au cobalt
US7012052B1 (en) Automatic dishwashing compositions comprising selected nonionic surfactants
US6326341B1 (en) Low foaming automatic dishwashing compositions
CA2264945C (fr) Compositions faiblement moussantes pour lave-vaisselle
EP0925342B1 (fr) Compositions pour lave-vaisselle, contenant des tensioactifs non ioniques faiblement moussants et agissant en conjonction avec des enzymes
EP1155105B1 (fr) Compositions detergentes pour lave-vaisselle comportant des surfactants non ioniques selectionnes
EP0998514B1 (fr) Compositions renfermant des tensioactifs a base d'alcools poly(oxyalkyles) coiffes par un ether
EP1190026A2 (fr) Compositions pour lave-vaisselle a systeme mixte de tensio-actifs
US5877134A (en) Low foaming automatic dishwashing compositions
US6013613A (en) Low foaming automatic dishwashing compositions
CA2363097C (fr) Procede d'elimination de taches sur une surface
MXPA01008463A (en) Automatic dishwashing compositions comprising mixed surfactants systems
MXPA00001141A (en) Compositions including ether-capped poly(oxyalkylated) alcohol surfactants

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ CZ DE DE DK DK DM EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2369120

Country of ref document: CA

Ref country code: CA

Ref document number: 2369120

Kind code of ref document: A

Format of ref document f/p: F

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2000 601115

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 09913870

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/008526

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2000908588

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2000908588

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWG Wipo information: grant in national office

Ref document number: 2000908588

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载