EP0518721B1 - Nichtwässriges, flüssiges, phosphatfreies und Enzyme enthaltendes Maschinengeschirrspülmittel - Google Patents

Nichtwässriges, flüssiges, phosphatfreies und Enzyme enthaltendes Maschinengeschirrspülmittel Download PDF

Info

Publication number
EP0518721B1
EP0518721B1 EP92401479A EP92401479A EP0518721B1 EP 0518721 B1 EP0518721 B1 EP 0518721B1 EP 92401479 A EP92401479 A EP 92401479A EP 92401479 A EP92401479 A EP 92401479A EP 0518721 B1 EP0518721 B1 EP 0518721B1
Authority
EP
European Patent Office
Prior art keywords
enzyme
weight
percent
dishwashing composition
nonaqueous liquid
Prior art date
Legal status (The legal status 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 status listed.)
Revoked
Application number
EP92401479A
Other languages
English (en)
French (fr)
Other versions
EP0518721A1 (de
Inventor
Patrick Durbut
Fahim Ahmed
Julian Drapier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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=27505508&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0518721(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US07/708,321 external-priority patent/US5169553A/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0518721A1 publication Critical patent/EP0518721A1/de
Application granted granted Critical
Publication of EP0518721B1 publication Critical patent/EP0518721B1/de
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

  • the enzymes in the detergent are maintained in a suitable environment, the enzymes will suffer a degradation during storage which will result in a product that will have a decreased initial activity.
  • the initial free water content of the composition should be as low a level as possible, and this low water content must be maintained during storage, since water will activate the enzymes. This activation will cause a decrease in the initial activity of the detergent composition.
  • the detergent After the detergent container is opened, the detergent will be exposed to the environment which contains moisture. During each instance that the detergent is exposed to the environment it could possibly absorb some moisture. This absorption occurs by components of the detergent composition absorbing moisture, when in contact with the atmosphere. This effect is increased as the container is emptied, since there will be a greater volume of air in contact with the detergent, and thus more available moisture to be absorbed by the detergent composition. This will usually accelerate the decrease in the activity of the detergent composition. The most efficient way to prevent a significant decrease in this activity is to start with an initial high activity of enzyme and to use components in the dishwashing composition which have a low hygroscopicity and a low alkalinity which will minimize any losses in activity as the detergent is being stored or used.
  • the stability of an enzymatic liquid, nonaqueous detergent can be improved by using an alkali metal silicate which has an alkali metal oxide: SiO2 weight ratio lower than 1:1 and of 1:2 to 1:3.4.
  • the individual components of the detergent composition should each have an initial free water content (unbound water at 100°C) of less than 10 percent by weight, more preferably less than 9 percent by weight, and most preferably less than 8 percent by weight.
  • the detergent composition will take-up moisture from the atmosphere.
  • the moisture content of the detergent composition as it is being packaged will be greater than about 1 percent by weight, preferably less than 4 percent by weight and most preferably less than 3 percent by weight.
  • Nonaqueous liquid dishwasher detergent compositions which contain enzymes can be made more stable and to have a high activity, if the initial free water content of the detergent composition is less than 6 percent by weight, more preferably less than 4 percent by weight and most preferably less than 3 percent by weight.
  • a key aspect is to keep the free water (non-chemically bonded water) in the detergent composition at a minimum. It is critical that water not be added to the composition. Absorbed and adsorbed water are two types of free water, and comprise the usual free water found in a detergent composition. Free water will have the affect of deactivating the enzymes.
  • the pH of a 1.0 wt% aqueous solution of the liquid detergent composition must be less than 10.5 more preferably less than 10.2, and most preferably less than 9.5. This low alkalinity of the dishwashing detergent will also increase the stability of the detergent composition which contains a mixture of enzymes, thereby providing a higher initial activity of the mixture of the enzymes and the maintenance of this initial high activity.
  • the free water content of the dishwashing detergent composition can be controlled to a large extent by using components that have a low initial water content and a low hygroscopicity.
  • the individual components should have a water content of less than 10.0 percent by weight, more preferably less than 9.0 percent by weight, and most preferably less than 8.0 percent by weight.
  • the organic components of the dishwashing detergent composition should have low hydroxyl group content to decrease the hydrogen bonding absorption of water.
  • the liquid carrier such as ethylene glycols or glycerols
  • nonaqueous relatively low hydroxyl content organics such as alcohol ethers and polyalkylene glycols can be used.
  • polyacid suspending agents normally used in liquid automatic dishwashing detergent compositions such as polyacrylic acid or salts of polyacrylic acids
  • polyacid/acid anhydride copolymers such as polyacrylic acid/acid anhydride copolymers.
  • Maleic anhydride is a suitable acid anhydride. The net result is a decreased hydroxyl group content which translates to a decreased hygroscopicity of the detergent composition which helps maintain the stability and the activity.
  • a major concern in the use of automatic dishwashing compositions is the formulation of phosphate-free compositions which are more safe to the environment while maintaining superior cleaning performance and dish care.
  • the present invention teaches the preparation and use of liquid automatic dishwashing compositions which are phosphate-free and have superior cleaning performance and dish care.
  • This invention is directed to producing a nonaqueous, phosphate-free, liquid enzyme-containing automatic dishwashing detergent composition that has an increased chemical stability and essentially a constant activity at wash operating temperatures of 40°C to 65°C, wherein the composition also can be used as a laundry pre-soaking agent. This is accomplished by controlling the alkalinity and the hygroscopicity of the detergent composition and using a mixture of enzymes.
  • An alkali metal silicate is used in the liquid dishwashing detergent compositions which will have a free water content of less than about 6 percent by weight, more preferably less than 4 percent by weight, and most preferably less than 3 percent by weight thought its usage.
  • the preferred builder system of the instant compositions comprises a mixture of a low molecular weight polyacrylate, sodium citrate and/or sodium carbonate. Furthermore, each of the organic components should have a low hydroxyl group content in order to decrease the potential hydrogen bonding absorption of water in the composition.
  • liquid automatic dishwashing compositions usually contain a low foaming surface-active agent, solvent which is usually water, a chlorine bleach, alkaline builder materials, and usually minor ingredients and additives.
  • a chlorine bleach requires special processing and storage precautions to protect composition components which are subject to deterioration upon direct contact with the active chlorine.
  • the stability of the chlorine bleach is also critical and raises additional processing and storage difficulties.
  • automatic dishwasher detergent compositions may tarnish silverware and damage metal trim on china as a result of the presence of a chlorine-containing bleach therein.
  • French Patent No. 2,102,851 to Colgate-Palmolive pertains to rinsing and washing compositions for use in automatic dishwashers.
  • the compositions disclosed have a pH of about 6 to 7 and contain an amylolytic and, if desired, a proteolytic enzyme, which have been prepared in a special manner from animal pancreas and which exhibit a desirable activity at a pH in the range of 6 to 7.
  • German Patent No. 2,038,103 to Henkel & Co. relates to aqueous liquid or pasty cleaning compositions containing phosphate salts, enzymes and an enzyme stabilizing compound.
  • US Patent No. 3,799,879 to Francke et al teaches a detergent composition for cleaning dishes, with a pH of from 7 to 9 containing an amylolytic enzyme, and in addition, optionally a proteolytic enzyme.
  • US Patent 4,162,987 to Maguire et al teaches a granular or liquid automatic dishwashing detergent which uses a proteolytic enzyme having a maximum activity at a pH of 12 as well as an amylolytic enzyme having a maximum activity at a pH of 8.
  • US Patent No 3,827,938 to Aunstrup et al discloses specific proteolytic enzymes which exhibit high enzymatic activities in highly alkaline systems. Similar disclosures are found in British Patent Specification No. 1,361,386, to Novo Terapeutisk Laboratorium A/S. British Patent Specification No. 1,296,839, to Novo Terapeutisk Laboratorium A/S, discloses specific amylolytic enzymes which exhibit a high degree of enzymatic activity in alkaline systems.
  • GB-A-2 194 546 discloses a nonaqueous liquid dishwashing enzyme containing composition comprising a high concentration of nonionic surfactant.
  • the stabilizing system is a clay based system.
  • EP-A-425 214 discloses an enzyme containing detergent composition having a content of 38.5% of nonionic surfactant when carried out in a nonaqueous liquid composition.
  • EP-A-028 849 pertains to a nonaqueous liquid detergent composition containing a nonionic surfactant in an amount of 5-45% by weight and a stabilizing system comprised of an at least partially hydrolyzed copolymer of maleic anhydride with ethylene or vinyl-methylether in the presence of a strongly alkaline material (p. 2, 1. 35 - p. 3, 1. 2).
  • the strongly alkaline material is present in an amount such that, when dissolved in distilled water at a concentration of 1.0% by weight, the pH of the solution is ⁇ 10 (p. 5, 1. 36 - p. 6, 1. 1).
  • the aforementioned prior art fails to provide a nonaqueous liquid automatic dishwashing detergent which is phosphate-free and contains a mixture of enzymes for the simultaneous degradation of both proteins and starches, wherein the combination of enzymes have a maximum activity at a pH of less than 9.5 as measured by Anson method and the liquid automatic dishwashing detergent has optimized cleaning performance in a temperature range of 40°C to 65°C.
  • the present invention relates to a nonaqueous liquid automatic dishwashing detergent compositions which comprise a nonionic surfactant, a nonaqueous liquid carrier, sodium silicate, a phosphate-free builder system, a stabilizing system, and a mixture of an amylase enzyme and a protease enzyme, wherein said dishwashing composition comprises in percent by weight : stabilizing system -- 0.5 - 7.0 % sodium silicate -- 3.0 - 20.0 % clay gel thickener -- 0.0 - 15.0 % hydroxypropyl cellulose polymer -- 0.0 - 0.6 % low molecular weight polyacrylate polymer -- 0.0 - 20.0 % liquid nonionic surfactant -- 2.0 - 15.0 % alkali metal carbonate -- 2.0 - 25.0 % sodium citrate -- 0.0 - 25.0 % anti-foaming agent -- 0.0 - 1.5 % protease enzyme -- 0.5 - 12.0 % amylase enzyme -- 0.3 - 6.0 % liquid carrier
  • liquid nonionic surfactants that can be used in the present nonaqueous liquid automatic dishwasher detergent compositions are well known. A wide variety of the these surfactants can be used.
  • the nonionic synthetic organic detergents are generally described as ethoxylated propoxylated fatty alcohols which are low-foaming surfactants and are possibly capped, characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide and/or propylene oxide (hydrophilic in nature).
  • any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent.
  • the length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.
  • Typical suitable nonionic surfactants are those disclosed in US Patent Nos. 4,316,812 and 3,630,929.
  • the nonionic detergents that are used are the low-foaming polyalkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety.
  • a preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 15.
  • the higher alkanol is a high fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mole.
  • the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, usually being major (more than 50%) portion.
  • the alkanol is of 12 to 15 carbon atoms and which contain 7 ethylene oxide groups per mole.
  • Useful nonionics are represented by the low foam Plurafac® series from BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A(a C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide). Product B (a C13-C15 fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide). Particularly good surfactants are Plurafac® LF132 and LF231 which are capped nonionic surfactants.
  • liquid nonionic surfactant that can be used is sold under the tradename Lutensol® SC 9713.
  • Synperonic® nonionic surfactant from ICI such as synperonic® LF/D25 are especially preferred nonionic surfactants that can be used in the nonaqueous liquid automatic dishwasher detergent compositions of the instant invention.
  • Neodol® 25-7 and Neodol® 23-6.5 are made by Shell Chemical Company, Inc.
  • the former is a condensation product of a mixture of higher fatty alcohols averaging 12 to 13 carbon atoms and the number of ethylene oxide groups present averages 6.5.
  • the higher alcohols are primary alkanols.
  • Other examples of such detergents include Tergitol® 15-S-7 and Tergitol® 15-S-9 (registered trademarks), both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp.
  • the former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.
  • nonionic detergent also useful in the present compositions as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 11.
  • higher molecular weight nonionics such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 11.
  • Neodol 45-11 are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 11.
  • Such products are also made by Shell Chemical Company.
  • the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol.
  • the alkylpolysaccharides surfactants which are also useful alone or in conjunction with the aforementioned surfactants and have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from 1.5 to 10, preferably from 1.5 to 4, and most preferably from 1.6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl, and/or galactosyl units). Mixtures of saccharide moieties may be used in the alkylpolysaccharide surfactants.
  • the number x indicates the number of saccharide units in a particular alkylpolysaccharide surfactant.
  • x can only assume integral values.
  • any physical sample can be characterized by the average value of x and this average value can assume non-integral values.
  • the values of x are to be understood to be average values.
  • the hydrophobic group (R) can be attached at the 2-, 3-, or 4- positions rather than at the l-position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside).
  • attachment through the 1-position i.e., glucosides, galactosides, fructosides, etc.
  • additional saccharide units are predominately attached to the previous saccharide unit's 2-position.
  • Attachment through the 3-, 4-, and 6-positions can also occur.
  • the preferred alkoxide moiety is ethoxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 20, preferably from 10 to 16 carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to about 30, preferably less than 10, most preferably 0, alkoxide moieties.
  • Suitable alkyl polysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof.
  • the alkyl monosaccharides are relatively less soluble in water than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosaccharides are solubilized to some extent.
  • the use of alkylmonosaccharides in admixture with alkylpolysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkylpolysaccharides are alkylpolyglucosides having the formula: R2O(C n H 2n O)r(Z) x wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to about 10, preferable 0; and x is from 1.5 to about 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7.
  • a long chain alcohol R2OH
  • an acid catalyst to form the desired glucoside
  • the alkylpolyglucosides can be prepared by a two step procedure in which a short chain alcohol (R1OH) an be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside.
  • a short chain alcohol C1 ⁇ 6
  • R2OH longer chain alcohol
  • the short chain alkylglucoside content of the final alkylpolyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkylpolygluco
  • the amount of unreacted alcohol (the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is preferably less than 2%, more preferably less than 0.5% by weight of the total of the alkylpolysaccharide. For some uses it is desirable to have the alkylmonosaccharide content less than 10%.
  • alkylpolysaccharide surfactant is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkylpolysaccharide surfactants.
  • alkylpolyglucoside is used to include alkyl- polyglycosides because the stereo chemistry of the saccharide moiety is changed during the preparation reaction.
  • APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA.
  • APG 625 has: a pH of 6-8(10% of APG 625 in distilled water); a specific gravity at 25°C of l.l grams/ml; a density at 25°C of 9.1 kgs/gallons; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
  • Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can be obtained by the use of such mixtures.
  • the liquid nonaqueous nonionic surfactant has dispersed therein a builder system which comprises a mixture of phosphate-free particles which is a builder salt and a low molecular weight polyacrylate.
  • a preferred solid builder salt is an alkali metal carbonate such as sodium carbonate or sodium citrate or a mixture of sodium carbonate and sodium citrate. When a mixture of sodium carbonate and sodium citrate is used, a weight ratio of sodium carbonate to sodium citrate is 9:1 to 1:9, more preferably 3:1 to 1:3.
  • builder salts which can be mixed with the sodium carbonate and/or sodium citrate are gluconates, phosphonates, and nitriloacetic acid salts.
  • low molecular weight polyacrylates having a molecular weight of 1,000 to 100,000, more preferably 2,000 to 80,000.
  • Preferred low molecular weight polyacrylate are Sokalan tm CP45 and Sokalan tm CP5 manufactured by BASF and having a molecular weight of 70,000.
  • Another preferred low molecular weight polyacrylate is Acrysol tm LMW45ND manufactured by Rohm and Haas and having a molecular weight of 4,500.
  • Sokalan tm CP45 is a copolymer of a polyacid and an acid anhydride. Such a material should have a water absorption at 38°C and 78 percent relative humidity of less than 40 percent and preferably less than 30 percent.
  • the builder is commercially available under the tradename of Sokalan tm CP45. This is a partially neutralized copolymer of methacrylic acid and maleic acid anhydride sodium salt.
  • Sokalan tm CP5 is the totally neutralized copolymer of methacrylic acid and maleic acid anhydride. Sokolan tm CP45 is classified as a suspending and anti-deposition agent.
  • This suspending agent has a low hygroscopicity as a result of a decreased hydroxyl group content.
  • An objective is to use suspending and anti-redeposition agents that have a low hygroscopicity.
  • Copolymerized polyacids have this property, and particularly when partially neutralized.
  • Acusol tm 640ND provided by Rohm & Haas is another useful suspending and anti-redepositing agent.
  • Another builder is Sokalan tm 9786X which is a copolymer of maleic acid and acrylic acid with a molecular weight of 70,000.
  • the alkali metal silicates are useful builder salts which also function to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts.
  • Sodium silicates of Na2O/SiO2 ratios of from 1.6:1 to 1:3.4 especially 1:1 to 1:2.8 are preferred. Potassium silicates of the same ratios can also be used.
  • the preferred alkali metal silicates are sodium disilicate (hydrated), sodium disilicate (anhydrous), sodium metasilicate and mixture thereof, wherein the preferred silicate is hydrated disilicate.
  • aluminosilicates both of the crystalline and amorphous type.
  • Various crystalline zeolites i.e. alumino-silicates
  • U.S. Patent No. 4,409,136 and Canadian Patent No. 1,087,477.
  • An example of amorphous zeolites useful herein can be found in Belgium Patent No. 835,351.
  • the zeolites generally have the formula (M2O) x (Al2O3) y (SiO2) x wH2O wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium.
  • a typical zeolite is type A or similar structure, with type 4A particularly preferred.
  • the preferred aluminosilicates have calcium ion exchange capacities of 200 milliequivalents per gram or greater, e.g. 400 meq/g.
  • the alkali metal silicates are useful anti-corrosion agents which function to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts.
  • Sodium silicates of Na2O/SiO2 ratios of from 1:1 to 1:3.4 especially 1:2 to 1:3 are preferred. Potassium silicates of the same ratios can also be used.
  • the preferred silicates are sodium disilicate (hydrated or anhydrous) and sodium metasilicate.
  • the thickening agents that can be used to ensure the physical stability of the suspension and viscosity enhancement are those that will swell and develop thixotropic properties in a nonaqueous environment. These include organic polymeric materials and inorganic and organic modified clays. Essentially, any clay can be used as long as it will swell in a nonaqueous medium and develop thixotropic properties.
  • a preferred clay is bentonite.
  • a swelling agent is used with the bentonite clay. The preferred swelling agent is a combination of propylene carbonate and tripropylene glycol methyl ether. However, any other substance that will cause bentonite to swell in a nonaqueous environment and thus develop thixotropic properties can be used.
  • any compatible anti-foaming agent can be used.
  • Preferred anti-foaming agents are silicone anti-foaming agents. These are alkylated polysiloxanes and include polydimethyl siloxanes, polydiethyl siloxanes, polydibutyl siloxanes, phenyl methyl siloxanes, dimethyl silanated silica, trimethysilanated silica and triethylsilanated silica.
  • Suitable anti-foaming agents are Silicone L7604 and TP201 from Union Carbide.
  • Another suitable anti-foaming agent is Silicone DB100 from Dow Corning used at 0.2 to 1.0 weight %, sodium stearate used at a concentration level of 0.5 to 1.0 weight% and LPKN 158 (phosphoric ester) sold by BASF used at a concentration level of 0 to 1.5 weight percent, more preferably 0.2 to 1.0 weight percent.
  • the perfumes that can be used include lemon perfume and other natural scents.
  • any opacifier pigment that is compatible with the remaining components of the detergent formulation can be used.
  • a useful and preferred opacifier is titanium dioxide at a concentration level of 0 to 1.5 weight percent.
  • the nonaqueous liquid carrier materials that can be used for the liquid automatic dishwashing detergent compositions are contained in the composition at a concentration level of at least 40 wt. percent to 65 wt. percent, more preferably, at least 45 wt. percent to 60 wt. percent, are those that have a low hygroscopicity. These include the higher glycols, polyglycols, and glycol ethers.
  • Suitable substances are propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol methyl ether acetate (PMA), dipropylene glycol methyl ether acetate (DPMA), ethylene glycol n-butyl ether and ethylene glycol n-propyl ether.
  • a preferred nonaqueous carrier of the instant invention is polyethylene glycol 200 (PEG200) or polyethylene glycol 300 (PEG300).
  • solvents are ethylene oxide/propylene oxide, liquid random copolymer such as Synalox® solvent series from Dow Chemical (e.g. Synalox® 50-50B).
  • suitable solvents are propylene glycol ethers such as PnB, DPnB and TPnB (propylene glycol mono n-butyl ether, dipropylene glycol and tripropylene glycol mono n-butyl ethers sold by Dow Chemical under the tradename Dowanol®.
  • tripropylene glycol mono methyl ether tripropylene glycol mono methyl ether
  • Another useful series of solvents are supplied by CGA Biochem, b.v. of Holland such as Plurasolv®ML, Plurasolv®EL(s), Plurasolv®EL, Plurasolv®IPL and Plurasolvo®BL.
  • PEG solvent with Synalox® or PnB, DPnB, TPnB and TPM solvents are also useful .
  • Preferred mixtures are PEG 300/Synalox® 50-50B and PEG 300/TPnB in weight ratios of 95:5 to 20:80, more preferably of 90:10 to 50:50.
  • the system used in the instant compositions to ensure phase stability comprises a finely divided silica such as Cab-o-Sil® M5, Cab-o-Sil® EH5, Cab-o-Sil® TS720 or Aerosil® 200 which are used at a concentration level of 0.1 to 4.0 weight percent, more preferably 0.5 to 3.0 weight%.
  • a finely divided silica such as Cab-o-Sil® M5, Cab-o-Sil® EH5, Cab-o-Sil® TS720 or Aerosil® 200 which are used at a concentration level of 0.1 to 4.0 weight percent, more preferably 0.5 to 3.0 weight%.
  • Also employed as a stabilizing system are mixtures of finely divided silica such as Cab-o-Sil® and nonionic associative thickeners such as Dapral® T210, T212 (Akzo) which are low molecular weight dialkyl polyglycol ethers with a dumbbell-like structure or Pluracol® TH 916 and TH 922 (BASF) associative thickeners having star-like structure with a hydrophilic core and hydrophobic tail. These thickeners are used at concentration levels of 0 to 5.0 weight percent together with 0.5 to 2.0 weight percent of finely divided silica.
  • the detergent composition of the present invention can possibly include a peroxygen bleaching agent at a concentration level of 1 to 15 wt. percent.
  • the oxygen bleaching agents that can be used are alkali metal perborate, percarbonate, perphthalic acid, and potassium monopersulfate.
  • a preferred compound is sodium perborate monohydrate.
  • the peroxygen bleaching compound is preferably used in admixture with an activator thereof. Suitable activators are those disclosed in U.S. Patent No. 4,264,466 or in column 1 of U.S. Patent No. 4,430,244. Polyacrylated compounds are preferred activators. Suitable preferred activators are tetraacetyl ethylene diamine ("TAED"), pentaacetyl glucose and ethylidene benzoate acetate.
  • TAED tetraacetyl ethylene diamine
  • the activator which is present at a concentration of 0.5 to 5.0 wt. percent usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of high complexing power to inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.
  • Suitable sequestering agents include the sodium salts of nitroilotriacetic acid (NA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the tradename DEQUEST® 2066 and ethylene diamine tetramethylene phosphoric acid (EDITEMPA).
  • NA nitroilotriacetic acid
  • EDTA ethylene diamine tetraacetic acid
  • DETPA diethylene triamine pentaacetic acid
  • DTPMP diethylene triamine pentamethylene phosphonic acid
  • the sequestering agents can be used alone or in an admixture.
  • the detergent formulation also contains a mixture of a proteolytic enzyme and an amylotytic enzyme and optionally, a lipolytic enzyme that serves to attack and remove organic residues on glasses, plates, pots, pans and eating utensils.
  • Proteolytic enzymes attack protein residues, lipolytic enzymes fat residues and amylolytic enzymes starches.
  • Proteolytic enzymes include the protease enzymes subtilism, bromelin, papain, trypsin and pepsin.
  • Amylolytic enzymes include amylase enzymes.
  • Lipolytic enzymes include the lipase enzymes.
  • the preferred amylase enzyme is available under the name Maxamyl®, derived from Bacillus licheniformis and is available from Gist-Brocades of the Netherlands in the form of a nonaqueous slurry (18 wt. % of enzyme) having an activity of 40,000 TAU/g.
  • One of the preferred protease enzyme is available under the name Maxacal® derived from Bacillus alcalophilus, and is supplied by Gist-Brocades, of the Netherlands in a nonaqeous slurry activity of 1,000,000 ADU/g.
  • Preferred enzyme activities per wash are Maxacal®-420-840 KDU per wash and Maxamyl®-4,000-8,000 TAU per wash.
  • Maxapem® 15 or Maxapem® 42 is a high alkaline mutant proteolytic enzyme derived from Bacillus alcalophylus, and is supplied by Gist-Brocades, of the Netherlands in a nonaqueous slurry (5.55 wt % of enzyme/activity of about 390,000 ADE/g).
  • Preferred enzyme activities per wash are Maxapem® 42-420-840 KDU per wash.
  • Preferred enzyme activities per wash are Maxapem® 42-420-840 KDU per wash and Maxamyl®-4,000-8,000 TAU per wash.
  • Maxatase® derived from a novel Bacillus strain designated "PB92" wherein a culture of the Bacillus is deposited with the Laboratory for Microbiology of the Technical University of Delft and has the numner OR-60, is supplied by Gist-Brocades, of the Netherlands in a nonaqueous slurry (22 wt.% of enzyme/activity of about 4000,000 Du/g).
  • Preferred enzyme activities per wash are Maxatase®-100-800 KDU per wash.
  • the weight ratio of the slurry of the proteolytic enzyme to the amylolytic in the nonaqueous liquid automatic dishwasher detergent compositions is 6:1 to 1:1, and more preferably 5:1 to 1.1:1.
  • the protease enzyme is Maxacal® and the amylase enzyme is Maxamyl® amylase enzyme, a weight ratio of said protease enzyme to said amylase enzyme being 6:1 to 1:1, the detergent dishwashing composition (1% aqueous solution) having a pH of less than 10.2.
  • the protease enzyme is Maxapem® 15 or Maxapen® 42 Protease enzyme and the amylase enzyme is Maxamyl® amylase enzyme, a weight ratio of the protease enzyme to the amylase enzyme being 6:1 to 1:1, the pH of the detergent dishwashing composition (1% aqueous solution) being less than 10.0.
  • the protease enzyme is Maxatase® Protease enzyme and the amylase enzyme is Maxamyl® amylase enzyme, a weight ratio of the protease enzyme to the amylase enzyme being 25:1 to 1:1, the pH of the detergent dish-washing composition (1% aqueous solution) being less than 11.
  • the detergent composition can have a fairly wide ranging composition.
  • the surfactant can comprise 2 to 12 percent by weight of the composition, more preferably 2 to 12 percent by weight, and most preferably 4 to 12 percent by weight.
  • the anti-foaming agent will be present in an amount of 0 to 1.5 percent by weight, more preferably 0.1 to 1.2 percent by weight and most preferably 0.3 to 1 percent by weight.
  • the builder system which is preferably sodium citrate, and more preferably sodium carbonate or a mixture of sodium carbonate and sodium citrate in a weight ratio of 9:1 to 1:9, more preferably 3:1 to 1:3, is present in an amount of 0 to 15 percent by weight, more preferably 4 to 20 percent by weight and most preferably 5 to 15 percent by weight in the detergent composition.
  • the builder system also preferably contains the low molecular weight noncrosslinked polyacrylate type polymer at a concentration level of 0 to 25 weight percent, more preferably 1.0 to 20 weight percent and most preferably 2 to 15 weight percent.
  • the thickener that can be used to provide phase stability to the detergent composition is preferably a bentonite clay gel which is a mixture of propylene carbonate and tripropylene glycol monomethyl ether (TPM) and Bentone® NL27. It is present in an amount of 0 to 15 percent by weight, more preferably 5 to 12 percent by weight and most preferably 7 to 10 percent by weight. Propylene carbonate in the gel will be present in an amount of 2 to 4 percent by weight, and the TPM is present at 80 to 90 weight percent. Also one can employ a bentonite clay gel/hydroxypropyl cellulose polymer.
  • TPM tripropylene glycol monomethyl ether
  • the alkali silicate which is a corrosion inhibitor, wherein sodium disilicate (hydrated) is preferred, will be present in an amount of 3 to 20 percent by weight, more preferably 3 to 15 percent by weight and most preferably 6 to 12 percent by weight.
  • the opacifier pigment will be present in the composition in an amount of 0 to 1.0 percent by weight, more preferably 0.1 to 1.0 percent by weight and most preferably 0.4 percent by weight.
  • the preferred stabilizing system are Cab-o-Sil® M5 and Cab-o-Sil® EH5 which are present at a preferred concentration of 0 to 3.0 weight percent, more preferably 0.1 to 3.0 weight percent, and most preferably 0.3 to 2.5 weight percent.
  • the enzymes will be present in the composition in an amount in slurry form (18 wt% enzyme powder in PEG 400/PEG 4000 liquid carrier) of 0.8 to 16.0 percent by weight, more preferably 0.9 to 14.0 percent by weight, and most preferably 1.0 to 12.0 percent by weight.
  • the protease enzyme slurry will be comprised in the automatic dishwashing composition at 0.5 to 12.0 percent by weight, more preferably at 0.7 to 10.0 weight percent and most preferably at about 0.8 to 8.0 percent by weight.
  • the amylase enzyme will be comprised 0.3 to 6.0 percent by weight, more preferably 0.4 percent to 3.0 weight percent and most preferably 0.5 to 2.0 weight percent.
  • the lipase enzyme will be comprised at 0 to 8.0 percent by weight of the detergent composition.
  • a suitable lipase is Lipolase 100 SL from Novo Corporation.
  • Another useful lipase enzyme is Amano PS® lipase provided by Amano International Enzyme Co, Inc.
  • the lipase enzymes are especially beneficial in reducing grease residues and related filming problems on glasses and dishware.
  • perfumes and color will be comprised at 0.0 to 1.0 percent by weight of the detergent composition.
  • the remainder of the detergent composition will be comprised of the nonaqueous carrier. This will range from 15 to 65 weight percent, more preferably 25 to 57 weight percent, and most preferably 40 to 55 weight percent.
  • the detergent formulation is produced by combining the liquid components consisting of the carrier, surfactant and anti-foam agent and then adding the builder salt, suspending and anti-redeposition agent (copolymerized polyacrylic acid) and alkali metal silicate. This mixture is then ground in a ball mill to a particle size of less than 10 microns, and preferably to a size of 4 to 5 microns.
  • the enzyme mixture is then added. The enzymes preferably will be in a polyethylene glycol slurry. This enzyme mixture is mixed into the ground slurry. Then the thickener, phase stabilizing system, opacifiers, brighteners and perfumes are added. After a thorough mixing, the detergent composition is packaged.
  • the concentrated nonaqueous liquid nonionic automatic dishwashing detergent compositions of the present invention dispenses readily in the water in the dishwashing machine.
  • the presently used home dishwashing machines have a measured capacity for 40 ml to 60 ml or 40 grams to 80 grams of detergent. In normal use, for example, for a full load of dirty dishes 45 grams of powdered detergent are normally used.
  • the concentrated liquid nonionic detergent composition In accordance with the present invention only 20 ml to 35 ml of the concentrated liquid nonionic detergent composition is needed.
  • the normal operation of an automatic dishwashing machine can involve the following steps or cycles: washing, rinse cycles with cold water and rinse cycles with hot water. The entire wash and rinse cycles require about 80-90 minutes.
  • the temperature of the wash water in European dishwashers is 50°C to 65°C, depending on the chosen washing program, and the temperature of the rinse water is 65°C, whatever the performed dishwashing program.
  • the highly concentrated nonaqueous liquid automatic dishwashing detergent compositions exhibit excellent cleaning properties for protein residues such as egg and starchy carbohydrates residues such as oatmeal and minimizes the formation of spots and film on the dishware and glassware.
  • the phase stability of the builder salts, the polyacrylate type polymer and the alkali metal silicate in the composition during storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid ingredients to less than 100 microns, preferably less than 40 microns and more preferably to less than 10 microns.
  • the solid builders are generally supplied in particle sizes of about 100, 200 or 400 microns.
  • the nonionic liquid surfactant phase can be possibly mixed with the solid builders prior to carrying out the grinding operation.
  • the proportion of solid ingredients be high enough (e.g. at least 40%, such as 50%) that the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquid.
  • any remaining liquid nonionic surfactant can be added to the ground formulation.
  • Mills which employ grinding balls (ball mills) or similar mobile grinding elements give very good results.
  • For larger scale work a continuously operating mill in which there are 1 mm. or 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed e.g.
  • a CoBall mill or a Netzsch ball mill may be employed.
  • the detergent builder particles have a particle size distribution such that no more than 10% by weight of said particles have a particle size of more than 10 microns.
  • compositions without grinding wherein the particle size has a distribution of 60-120 microns.
  • the concentrated nonaqueous liquid nonionic surfactant detergent compositions were formulated from the following ingredients in the amounts specified.
  • compositions of the invention were evaluated for performance according to the following laboratory test methods.
  • Oatmeal soil was prepared by boiling 24 grams of Quaker Oats in 400 ml of tap water for ten minutes and then homogenized with a high shearing device (Ultraturax)®. 3 grams of this mixture were spread as thin film onto 19.05 cm (7.5 inch) china plates. The plates were aged for 2 hours at 80°C, and then stored overnight at room temperature.
  • Hardened egg soil was prepared by mixing egg yolk with an equal amount of 2.5N calcium chloride solution. 0.4 grams of this mixture was applied as a thin crosswise film to the usable surface of 19.05 cm (7.5inch) china plates.
  • Microwave egg soil was prepared by mixing hot egg yolk and cooked margarine with an homogenizer (Ultraturax® device). 5 grams of this mixture were spread as thin film onto 19.05 cm (7.5 inch) china plates, and the soiled plates were based afterwards for one minute in a microwave oven. The two type of egg soils were stored overnight at room temperature. Six plates of oatmeal and three plates of each egg were used per wash, together with six clean glasses. The twelve soiled plates and the six glasses were always placed in the same positions in the dishwasher at each run. In each test four different compositions were assessed according to a Latin Square procedure using a series of four dishwashers. Cleaning performance results for each composition are average of the four runs conducted in the four dishwashers.
  • the dishwasher load included each run six plates of oatmeal, three plates of hardened egg, three plates of microwave-egg, one dish of white sauce, one dish of rice, four glasses soiled with tomato juice four glasses soiled with tomato juice, four glasses soiled with cocoa and four soiled with milk.
  • Pieces of cutlery forks, knives and spoons, six each) were also included and soiled with porridge soil, rice and rice with cheese soils.
  • the dishwasher load included six clean plates in the lower basket, six clean glasses in the upper basket and sixteen plastic tiles in the cutlery basket.
  • the soil load was consisting of 50 g of a greasy soil mixture prepared by mixing mustard (42 weight %) white vinegar (33 wt. %), corn oil (15 wt. %) and lard (10 wt. %) altogether.
  • the upper basket containing the six glasses, the cutlery basket with the plastic tiles as well as the dishwasher filter elements were moved from one dishwasher to the following one, before conducting the next run.
  • Such a procedure was used to assess the performance of compositions on glasses and on plastic dishware surfaces under conditions of repeated washer in the presence of said greasy soil mixture.
  • glasses were scored in a viewing box for global aspect, and filming and spotting performance according to the same 0 (bad performance) to 10 (perfectly clean glasses) scale as for the so-called soil cleaning test with the aid of reference glasses. Also plastic tiles were weighted after a series of four runs. A greasy build-up index was determined for each tested composition according to the equation [(P2-P1)/P1] X 10,000 with P1 being the weight of the sixteen clean plastic tiles and P2 the final weight of the sixteen tiles after four runs.
  • the concentrated nonaqueous liquid nonionic surfactant detergent compositions were formulated from the following ingredients in the amounts specified.
  • TABLE II A B PEG 300 Balance Balance SYNPERONIC® LFD25 8 8 SILICONE DB100 0.2 0.2 SODIUM DISILICATE (Anhydrous) 0 9.0 SODIUM DISILICATE (hydrated) 12.0 0 SODIUM CARBONATE 12.0 12.0 SOKALAN® CP45 8.0 8.0 MAXADEM® PROTEASE 9.0 9.0 (Activity 400,000 ADU/g MAXAMYL® AMYLASE (Activity 40,000 TAU/g) 0.8 0.8 CABOSIL® M5 2.0 2.0 PHYSICAL STABILITY -Phase separation in height% RT 6 weeks 0% 4°C 6 weeks 0% 35° C 6 weeks 1%
  • compositions of the invention were evaluated for performance according to the following laboratory test methods.
  • Oatmeal soil was prepared by boiling 24 grams of Quaker Oats in 400 ml of tap water for ten minutes and then homogenized with a high shearing device (Ultraturax®). 3 grams of this mixture were spread as thin film onto 19.05 cm (7.5 inch) china plates. The plates were aged for 2 hours at 80°C, and then stored overnight at room temperature.
  • Hardened egg soil was prepared by mixing egg yolk with an equal amount of 2.5N calcium chloride solution. 0.4 grams of this mixture was applied as a thin crosswise film to the usable surface of 19.05 cm (7.5 inch) china plates.
  • Microwave egg soil was prepared by mixing hot egg yolk and cooked margarine with an homogenizer (Ultraturax® device). 5 grams of this mixture were spread as thin film onto 19.05 cm (7.5 inch) china plates, and the soiled plates were based afterwards for one minute in a microwave oven. The two type of egg soils were stored overnight at room temperature. Six plates of oatmeal and three plates of each egg were used per wash, together with six clean glasses. The twelve soiled plates and the six glasses were always placed in the same positions in the dishwasher at each run. In each test four different compositions were assessed according to a Latin Square procedure using a series of four dishwashers. Cleaning performance results for each composition are average of the four runs conducted in the four dishwashers.
  • the dishwasher load included each run six plates of oatmeal, three plates of hardened egg, three plates of microwave-egg, one dish of white sauce, one dish of rice, four glasses soiled with tomato juice four glasses soiled with tomato juice, four glasses soiled with cocoa and four soiled with milk.
  • Pieces of cutlery forks, knives and spoons, six each) were also included and soiled with porridge soil, rice and rice with cheese soils.
  • the dishwasher load included six clean plates in the lower basket, six clean glasses in the upper basket and sixteen plastic tiles in the cutlery basket.
  • the soil load was consisting of 50 g of a greasy soil mixture prepared by mixing mustard (42 weight %) white vinegar (33 wt. %), corn oil (15 wt. %) and lard (10 wt. %) altogether.
  • the upper basket containing the six glasses, the cutlery basket with the plastic tiles as well as the dishwasher filter elements were moved from one dishwasher to the following one, before conducting the next run.
  • Such a procedure was used to assess the performance of compositions on glasses and on plastic dishware surfaces under conditions of repeated washer in the presence of said greasy soil mixture.
  • glasses were scored in a viewing box for global aspect, and filming and spotting performance according to the same 0 (bad performance) to 10 (perfectly clean glasses) scale as for the so-called soil cleaning test with the aid of reference glasses. Also plastic tiles were weighted after a series of four runs. A greasy build-up index was determined for each tested composition according to the equation [(P2-P1)/P1] X 10,000 with P1 being the weight of the sixteen clean plastic tiles and P2 the final weight of the sixteen tiles after four runs.
  • compositions of the invention were evaluated for performance according to the following laboratory test methods.
  • Oatmeal soil was prepared by boiling 24 grams of Quaker Oats in 400 ml of tap water for ten minutes and then homogenized with a high shearing device (Ultraturax®). 3 grams of this mixture were spread as thin film onto 19.05 cm (7.5 inch) china plates. The plates were aged for 2 hours at 80°C, and then stored overnight at room temperature.
  • Hardened egg soil was prepared by mixing egg yolk with an equal amount of 2.5N calcium chloride solution. 0.4 grams of this mixture was applied as a thin crosswise film to the usable surface of 19.05 cm (7.5 inch) china plates.
  • Microwave egg soil was prepared by mixing hot egg yolk and cooked margarine with an homogenizer (Ultraturax® device). 5 grams of this mixture were spread as thin film onto 19.05 cm (7.5) inch china plates, and the soiled plates were baked afterwards for one minute in a microwave oven. The two type of egg soils were stored overnight at room temperature. Six plates of oatmeal and three plates of each egg were used per wash, together with six clean glasses. The twelve soiled plates and the six glasses were always placed in the same positions in the dishwasher at each run. In each test four different compositions were assessed according to a Latin Square procedure using a series of four dishwashers. Cleaning performance results for each composition are average of the four runs conducted in the four dishwashers.
  • the dishwasher load included each run six plates of oatmeal, three plates of hardened egg, three plates of microwave-egg, one dish of white sauce, one dish of rice, four glasses soiled with tomato juice four glasses soiled with tomato juice, four glasses soiled with cocoa and four soiled with milk.
  • Pieces of cutlery forks, knives and spoons, six each) were also included and soiled with oatmeal soil, rice and rice with cheese soils.
  • the dishwasher load included six clean plates in the lower basket, six clean glasses in the upper basket and sixteen plastic tiles in the cutlery basket.
  • the soil load was consisting of 50 g of a greasy soil mixture prepared by mixing mustard (42 weight %) white vinegar (33 wt. %), corn oil (15 wt. %) and lard (10 wt. %) altogether.
  • the upper basket containing the six glasses, the cutlery basket with the plastic tiles as well as the dishwasher filter elements were moved from one dishwasher to the following one, before conducting the next run.
  • Such a procedure was used to assess the performance of compositions on glasses and on plastic dishware surfaces under conditions of repeated washer in the presence of said greasy soil mixture.
  • glasses were scored in a viewing box for global aspect, and filming and spotting performance according to the same 0 (bad performance) to 10 (perfectly clean glasses) scale as for the so-called soil cleaning test with the aid of reference glasses. Also plastic tiles were weighted after a series of four runs. A greasy build-up index was determined for each tested composition according to the equation [(P2-P1)/P1] X 10,000 with P1 being the weight of the sixteen clean plastic tiles and P2 the final weight of the sixteen tiles after four runs.

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)
  • Enzymes And Modification Thereof (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Pyrane Compounds (AREA)

Claims (11)

  1. Nichtwäßrige, flüssige, phosphat- und chlorbleichfreie Geschirrspülzusammensetzung, die eine binäre Mischung aus Proteaseenzym und Amylaseenzym enthält, wobei die Geschirrspülzusammensetzung in Gew.-% umfaßt: - Phasenstabilisierungssystem, das 0,5 bis 4,0 % feinteiliges Siliciumdioxid umfaßt - Natriumsilikat 3,0 bis 20,0 % - Polyacrylatpolymer mit niedrigem Molekulargewicht (1000 bis 100 000) 0,0 bis 20,0 % - flüssiges nichtionisches Tensid 2,0 bis 12,0 % - Alkalimetallcarbonat 2,0 bis 25,0 % - Natriumcitrat 0,0 bis 15,0 % - Antischaummittel 0,0 bis 1,5 % - Proteaseenzym 0,5 bis 12,0 % - Amylaseenzym 0,3 bis 6,0 % - flüssiger Träger 40 bis 65 %
    wobei der flüssige Träger ausgewählt ist aus höheren Glykolen, Polyglykolen und Glykolethern, der Gehalt an freiem Wasser kleiner als etwa 6 Gew.-% ist und der pH-Wert einer 1,0 gew.-%igen wäßrigen Lösung der Zusammensetzung kleiner als 9,5 ist.
  2. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, bei der die Geschirrspülzusammensetzung ferner Lipaseenzym enthält.
  3. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, bei der die Geschirrspülzusammensetzung einen Gehalt an freiem Wasser kleiner als 4 Gew.-% aufweist.
  4. Nichtwäßrige, flüssige Geschirrspülzussammensetzung nach Anspruch 1, die eine effektive Menge eines oder mehrerer Hilfsmittel ausgewählt aus der Gruppe bestehend aus Antiverkrustungsmitteln, Sauerstoffbleichmitteln, Bleichmittelaktivatoren, Sequestriermitteln, Antikorrosionsmitteln, Antischaummitteln, Trübungsmitteln und Parfümen umfaßt.
  5. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, die Alkalimetallperborat enthält.
  6. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 6, die Alkalimetallperborataktivator enthält.
  7. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, die 0,1 bis 1,2 Gew.-% Antischaummittel enthält.
  8. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, bei der das Proteaseenzym Maxacal® Proteaseenzym ist und das Amylaseenzym Maxamyl® Amylaseenzym ist, wobei das Gewichtsverhältnis des Proteaseenzyms zu dem Amylaseenzym 6 : 1 bis 1 : 1 beträgt.
  9. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, bei der das Proteaseenzym Maxapem® 15 oder Maxapem® 42 Proteaseenzym ist und das Amylaseenzym Maxamyl® Amylaseenzym ist, wobei das Gewichtsverhältnis des Proteaseenzyms zu dem Amylaseenzym 6 : 1 bis 1 : 1 beträgt.
  10. Nichtwäßrige, flüssige Geschirrspülzusammensetzung nach Anspruch 1, bei der das Proteaseenzym Maxatase® Proteaseenzym ist und das Amylaseenzym Maxamyl® Amylaseenzym ist, wobei das Gewichtsverhältnis des Proteaseenzyms zu dem Amylaseenzym 25 : 1 bis 1 : 1 beträgt.
  11. Verfahren zum Spülen von Geschirr in einer Geschirrspülmaschine, daß das Spülen des Geschirrs bei Betriebstemperaturen von 38 °C (100 °F) bis 60 °C (140 °F) mit einer Zusammensetzung gemäß Anspruch 1 umfaßt.
EP92401479A 1991-05-31 1992-05-29 Nichtwässriges, flüssiges, phosphatfreies und Enzyme enthaltendes Maschinengeschirrspülmittel Revoked EP0518721B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US70832091A 1991-05-31 1991-05-31
US70856691A 1991-05-31 1991-05-31
US07/708,321 US5169553A (en) 1991-05-31 1991-05-31 Nonaqueous liquid, phosphate-free, improved automatic dishwashing composition containing enzymes
US708566 1991-05-31
US708320 1991-05-31
US708321 1991-05-31
US83731692A 1992-02-10 1992-02-10
US837316 1992-02-10

Publications (2)

Publication Number Publication Date
EP0518721A1 EP0518721A1 (de) 1992-12-16
EP0518721B1 true EP0518721B1 (de) 1995-08-02

Family

ID=27505508

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92401479A Revoked EP0518721B1 (de) 1991-05-31 1992-05-29 Nichtwässriges, flüssiges, phosphatfreies und Enzyme enthaltendes Maschinengeschirrspülmittel

Country Status (9)

Country Link
EP (1) EP0518721B1 (de)
AT (1) ATE125863T1 (de)
AU (1) AU655274B2 (de)
CA (1) CA2069987A1 (de)
DE (1) DE69203795D1 (de)
FI (1) FI922487A (de)
NO (1) NO922046L (de)
NZ (1) NZ242843A (de)
PT (1) PT100537A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU667600B2 (en) * 1993-02-08 1996-03-28 Colgate-Palmolive Company, The Nonaqueous gelled automatic dishwashing composition containing enzymes
EP0694059B1 (de) * 1993-04-27 1999-01-13 The Procter & Gamble Company Flüssiges oder körniges maschinengeschirrspülmittel
CA2161083C (en) * 1993-04-27 2000-06-13 Eugene Steven Sadlowski Liquid or granular automatic dishwashing detergent compositions
TR28788A (tr) 1993-05-25 1997-03-25 Henkel Ecolab Gmbh & Co Ohg Makinayla bulasik temizlemege mahsus usul ve tertibat.
BR9508894A (pt) * 1994-09-06 1997-11-18 Johnson & Son Inc S C Composição de limpeza baseada em enzima líquida e processo de limpeza de uma superficie transportando sujeiras de alimento queimadas
GB2297978A (en) * 1995-02-15 1996-08-21 Procter & Gamble Detergent compositions containing amylase
ES2143777T3 (es) * 1995-08-25 2000-05-16 Henkel Kgaa Empleo de lipasas en agentes de baja alcalinidad para el fregado a maquina de la vajilla.
CZ417698A3 (cs) 1996-06-28 1999-06-16 The Procter & Gamble Company Nevodný čistící prostředek obsahující enzymy
EP0991746A1 (de) * 1997-06-27 2000-04-12 The Procter & Gamble Company Flüssige wasserfreie reinigungsmittelzusammensetzungen, enthaltend enzymteilchenmit verminderter dichte
DE19822939A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Nichtwäßrige viskose Geschirreinigungsmittel
WO2002008370A2 (en) * 2000-07-19 2002-01-31 The Procter & Gamble Company Cleaning composition
DE10009252A1 (de) 2000-03-01 2001-09-06 Henkel Kgaa Wärmendes Hautreinigungsgel
CA2415304A1 (en) * 2000-07-19 2002-01-24 The Procter & Gamble Company Gel form automatic dishwashing compositions, methods of preparation and use thereof
DE10153553A1 (de) 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
PL202632B1 (pl) * 2001-08-17 2009-07-31 Henkel Ag & Co Kgaa Środek do maszynowego natryskowego zmywania naczyń
US20080293607A1 (en) 2007-03-09 2008-11-27 Jones Brian E Alkaliphilic Bacillus Species alpha-Amylase Variants, Compositions Comprising alpha-Amylase Variants, And Methods of Use
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
WO2009149283A1 (en) 2008-06-06 2009-12-10 Danisco Us Inc. Saccharification enzyme composition
CA2726630A1 (en) 2008-06-06 2009-12-10 Danisco Us Inc. Production of glucose from starch using alpha-amylases from bacillus subtilis
WO2010036515A1 (en) 2008-09-25 2010-04-01 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
EP2491121A2 (de) 2009-10-23 2012-08-29 Danisco US Inc. Verfahren zur reduktion von blauem saccharid
DE102012107728A1 (de) * 2012-08-22 2014-02-27 Witty-Chemie Gmbh & Co. Kg Phosphorfreies Reinigungsmittel für Geschirrspülanlagen und Verfahren dafür
US10426719B2 (en) * 2016-12-20 2019-10-01 Colgate-Palmolive Company Oral care compositions and methods for whitening teeth

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2727463A1 (de) * 1976-06-24 1978-01-05 Procter & Gamble Reinigungsmittel, das insbesondere zur verwendung in geschirrspuelmaschinen geeignet ist
DE3065073D1 (en) * 1979-11-09 1983-11-03 Unilever Nv Non-aqueous, built liquid detergent composition and method for preparing same
DE3428834A1 (de) * 1984-08-04 1986-02-13 Henkel KGaA, 4000 Düsseldorf Geschirreinigungsmittel
US4753748A (en) * 1986-08-28 1988-06-28 Colgate-Palmolive Company Nonaqueous liquid automatic dishwashing detergent composition with improved rinse properties and method of use
GB8915658D0 (en) * 1989-07-07 1989-08-23 Unilever Plc Enzymes,their production and use
GB8923788D0 (en) * 1989-10-23 1989-12-13 Unilever Plc Enzymatic detergent compositions and their use
AU655261B2 (en) * 1991-05-31 1994-12-08 Colgate-Palmolive Company, The Nonaqueous liquid automatic dishwashing composition containing enzymes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Also Published As

Publication number Publication date
EP0518721A1 (de) 1992-12-16
PT100537A (pt) 1994-01-31
NO922046D0 (no) 1992-05-25
NZ242843A (en) 1995-03-28
AU1701692A (en) 1992-12-03
AU655274B2 (en) 1994-12-15
ATE125863T1 (de) 1995-08-15
CA2069987A1 (en) 1992-12-01
NO922046L (no) 1992-12-01
FI922487A (fi) 1992-12-01
DE69203795D1 (de) 1995-09-07
FI922487A0 (fi) 1992-05-29

Similar Documents

Publication Publication Date Title
EP0518721B1 (de) Nichtwässriges, flüssiges, phosphatfreies und Enzyme enthaltendes Maschinengeschirrspülmittel
EP0518719B1 (de) Enzyme enthaltendes nichtwässriges flüssiges Maschinengeschirrspülmittel
US5173207A (en) Powered automatic dishwashing composition containing enzymes
EP0518720B1 (de) Enzyme enthaltenes nichtwässriges flüssiges Maschinengeschirrspülmittel
US5169553A (en) Nonaqueous liquid, phosphate-free, improved automatic dishwashing composition containing enzymes
US5527483A (en) Nonaqueous gelled automatic dishwashing composition containing enzymes
US5510048A (en) Nonaqueous liquid, phosphate-free, improved autoamatic dishwashing composition containing enzymes
AU656375B2 (en) Powdered automatic dishwashing composition containing enzymes
AU667600B2 (en) Nonaqueous gelled automatic dishwashing composition containing enzymes
US5545344A (en) Nonaqueous liquid, improved automatic dishwashing composition containing enzymes
AU654184B2 (en) Improved phosphate-containing powder automatic dishwashing composition with enzymes
US5468411A (en) Powdered automatic dishwashing composition containing enzymes
US5318715A (en) Liquid automatic dishwashing composition containing two enzymes
US5618465A (en) Nonaqueous liquid automatic dishwashing composition containing enzymes
EP0516555A2 (de) Pulverförmige phosphatenthaltende Zusammensetzung mit Enzymen für Geschirrspülmaschinen
US5474699A (en) Phosphate containing powered automatic dishwashing composition with enzymes
US5693602A (en) Spray dried powered automatic dishwashing composition containing enzymes
AU655261B2 (en) Nonaqueous liquid automatic dishwashing composition containing enzymes
AU651686B2 (en) Nonaqueous liquid automatic dishwashing composition containing enzymes
IE921753A1 (en) Nonaqueous liquid, phosphate-free, improved automatic¹dishwashing composition containing enzymes
IE921750A1 (en) Improved phosphate-containing powder automatic dishwashing¹composition with enzymes
IE921758A1 (en) Nonaqueous liquid automatic dishwashing composition¹containing enzymes
IE921751A1 (en) "NONAQUEOUS LIQUID AUTOMATIC DISHWASHING COMPOSITION CONTAINING ENZYMES IE
CA2069854A1 (en) Powdered automatic dishwashing composition containing enzymes
IE921757A1 (en) Nonaqueous liquid automatic dishwashing composition¹containing enzymes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19921223

17Q First examination report despatched

Effective date: 19930408

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950802

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19950802

Ref country code: DK

Effective date: 19950802

Ref country code: BE

Effective date: 19950802

Ref country code: AT

Effective date: 19950802

REF Corresponds to:

Ref document number: 125863

Country of ref document: AT

Date of ref document: 19950815

Kind code of ref document: T

REF Corresponds to:

Ref document number: 69203795

Country of ref document: DE

Date of ref document: 19950907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19951102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19951103

Ref country code: DE

Effective date: 19951103

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960524

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19960531

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19960618

Year of fee payment: 5

26 Opposition filed

Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

Effective date: 19960502

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960529

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19981226