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EP0554943A2 - Waschmittelzusammensetzung - Google Patents

Waschmittelzusammensetzung Download PDF

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Publication number
EP0554943A2
EP0554943A2 EP93200217A EP93200217A EP0554943A2 EP 0554943 A2 EP0554943 A2 EP 0554943A2 EP 93200217 A EP93200217 A EP 93200217A EP 93200217 A EP93200217 A EP 93200217A EP 0554943 A2 EP0554943 A2 EP 0554943A2
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
alkyl
composition according
surfactant
group
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.)
Granted
Application number
EP93200217A
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English (en)
French (fr)
Other versions
EP0554943B1 (de
EP0554943A3 (en
Inventor
James William Unilever Res. Vlaardingen Gordon
Antoine Pierre A. F. Unilever Research Rocourt
Rudolf Cornelis S. Verheul
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Unilever NV
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Unilever NV
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Publication date
Priority claimed from GB929202237A external-priority patent/GB9202237D0/en
Application filed by Unilever NV filed Critical Unilever NV
Publication of EP0554943A2 publication Critical patent/EP0554943A2/de
Publication of EP0554943A3 publication Critical patent/EP0554943A3/en
Application granted granted Critical
Publication of EP0554943B1 publication Critical patent/EP0554943B1/de
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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
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • 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 present invention relates to an aqueous liquid detergent product particularly adapted for use in a machine dishwasher.
  • Liquid automatic dishwasher detergent compositions both aqueous and non-aqueous, have recently received much attention and the aqueous products have achieved commercial popularity.
  • a mild and yet quite effective aqueous liquid machine dishwashing detergent composition can be formulated based on certain surfactants and proteolytic enzymes wherein there is an apparent synergistic effect between the active and the protease enzyme, especially in the removal of protein soil.
  • glycosides in detergent compositions has been disclosed in a number of documents.
  • WO 86/05187 discloses laundry detergent compositions comprising glycoside surfactant and enzyme. Various enzymes are mentioned.
  • DE 38 33 047 discloses acidic powdered dishwashing compositions containing alkyl glycoside in combination with other surfactant and amylase. These compositions are acidic and have solution pH below 6.
  • a chlorine bleach-free aqueous liquid machine dishwashing detergent composition comprising:
  • this invention provides a method of washing crockery and/or glassware comprising exposing the crockery and/or glassware to a mixture of water and a detergent composition as specified above.
  • the invention provides use of such a composition in machine dishwashing.
  • Protease can, for example, be used in an amount ranging from about the order of 0.0002 to about the order of 0.05 Anson units per gram of the detergent composition, preferably 0.001 to 0.025 Anson units. Expressed in other units, the protease can also be included in the compositions in amounts of the order of from about 0.5 to 100 GU/mg of the detergent composition. Preferably, the amount ranges from 1 to 50, and particularly preferably from 2 or even 5 to 15 or 20 GU/mg of composition.
  • a GU is a Glycine Unit, defined as the proteolytic enzyme activity which, under standard conditions, during a 15-minute incubation at 40°C with N-acetyl casein as substrate, produces an amount of NH2-group equivalent to 1 micromole of glycine.
  • KNPU kilo Novo units
  • protease enzyme to be used in the present compositions are the subtilisin varieties sold as Savinase (TM of Novo-Nordisk A/S) or Maxacal (TM of Gist-Brocades/IBIS) or as Opticlean (ex MKC) or AP122 (ex Showa Denko), which has pI approximately 10.
  • Other useful examples of proteases include Maxatase, Esperase, Alcalase (Trade Marks), protinase K and subtilisin BPN'. Protinase K can also be used.
  • G is a residue of a pentose or hexose
  • R'O is an alkoxy group
  • x is at least unity
  • R is an organic hydrophobic group which is preferably aliphatic, either saturated or unsaturated, notably straight or branched alkyl, alkenyl, hydroxyalkyl or hydroxyalkenyl.
  • R may include an aryl group, for example alkyl-aryl, alkenyl-aryl and hydroxyalkyl-aryl. It is envisaged that R may be from 6 to 20 carbon atoms.
  • R is alkyl or alkenyl of 7 to 14 or 16 carbon atoms, especially 7 to 12.
  • the value of t in the general formula above is preferably zero, so that the -(R'O) t - unit of the general formula is absent. In that case the general formula becomes : RO(G) x or If t is non-zero, it is preferred that R'O is an ethylene oxide residue. Other possibilities are propylene oxide and glycerol residues. If the parameter t is non-zero so that R'O is present, the value of t (which may be an average value) will preferably lie in the range from 0.5 to 10.
  • the group G is typically derived from fructose, glucose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose and/or ribose.
  • the G is provided substantially exclusively by glucose units.
  • Intersaccharide bonds may be from a 1-position to a 2, 3, 4 or 6-position of the adjoining saccharide.
  • Hydroxyl groups on sugar residues may be substituted., e.g. etherified with short alkyl chains of 1 to 4 carbon atoms.
  • a sugar residue bears no more than one such substituent.
  • x which is an average, is usually termed the degree of polymerization. Desirably x varies between 1 and 8. Values of x may lie between 1 and 3, especially 1 and 1.8.
  • Alkyl polyglycosides of formula RO(G) x i.e. a formula as given above in which t is zero, are available from BASF and Henkel.
  • Alkyl polyglycosides of particular interest have x in the narrow range from 1 or 1.2 up to 1.4 or especially 1.3. If x exceeds 1.3, it preferably lies in the range from 1.3 or 1.4 to 1.8.
  • R is C8 to C14 alkyl or alkenyl.
  • O-alkanoyl glucosides are described in International Patent Application WO 88/10147 (Novo Industri A/S).
  • the surfactants described therein are glucose esters with the acyl group attached in the 3- or 6-position such as 3-0-acyl-D-glucose or 6-0-acyl-D-glucose.
  • 6-0-alkanoyl glucosides in which the alkanoyl group incorporates an alkyl or alkenyl group having from 7 to 13 preferably 7, 9 or 11 carbon atoms.
  • the glucose residue may be alkylated in its 1-position with an alkyl group having from 1 to 4 carbon atoms, such as ethyl or isopropyl. Alkylation in the 1-position enables such compounds to be prepared by regiospecific enzymatic synthesis as described by Bjorkling et al. (J. Chem. Soc., Chem. Commun. 1989 p934).
  • esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
  • Preferred anionic surfactants are one or a mixture of: primary alkyl sulphate of formula: R1OSO3M where R1 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilising cation, fatty acid ester sulphonate of formula where R2 is an alkyl group of 6 to 16 carbon atoms, R3 is an alkyl group of 1 to 4 carbon atoms and M is a solubilising cation, alkyl benzene sulphonate of formula where R4 is an alkyl group of 10 to 16 carbon atoms and M is a solubilising cation, alkyl ether sulphate of formula R1O(CH2CH2O) n SO3M where R1 is a primary alkyl group of 8 to 18 carbon atoms, n has an average value in the range from 1 to 6 and M is a solubilising cation.
  • R1OSO3M where R1 is a primary
  • surfactant is primary alkyl sulphate.
  • solubilising cation may be a range of cations which are general monovalent and confer water solubility.
  • Alkali metal notably sodium, is especially envisaged.
  • Other possibilities are ammonium and substituted ammonium, such as trialkanolammonium.
  • the alkyl group R1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R1 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R1 is coconut alkyl, for example.
  • solubilising cation M may be a range of cations as discussed above for alkyl sulphate.
  • the group R2 may have a mixture of chain lengths. Preferably at least two thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety: is derived from a coconut source, for instance.
  • the group R3 may be any C1 to C4 alkyl group.
  • Straight chain alkyl may be preferred, notably methyl or ethyl.
  • the group R4 may be a mixture of chain lengths. Preferred are straight chains of 11 to 14 carbon atoms.
  • alkyl ether sulphate R1O(CH2CH2O) n SO3M the group R1 is as discussed for alkyl sulphate.
  • n has an average value of 2 to 5.
  • Ethoxylated fatty alcohol may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above. However, if it is used alone than the fatty alcohol must be of limited chain length so that average chain lengths of the alkyl group R in the general formula: RO(CH2CH2O) n H is from 6 to 12 carbon atoms. This is preferred in any event, and especially preferred if the weight of anionic surfactant is less than half the weight of ethoxulated fatty alcohol.
  • group R may have chain lengths in a range from 9 to 11 carbon atoms.
  • An ethoxylated fatty alcohol normally is a mixture of molecules with different numbers of ethylene oxide residues. Their average number, n, together with the alkyl chain length, determines whether the ethoxylated fatty alcohol has a hydrophobic character (low HLB value) or a hydrophilic character (high HLB value). For this invention the HLB value should be 10.5 or greater. This requires the average value of n to be at least 4, and possibly higher.
  • the numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation.
  • Particularly preferred ethoxylated fatty alcohols have a group R which has 9 to 11 carbon atoms while n is from 5 to 8.
  • the above surfactant may possibly be accompanied by some other detergent active, usually in a lesser quantity.
  • the amount of any other detergent surfactant will be no more than one third of the total weight of detergent surfactant present, or even no more than one quarter.
  • surfactant may be anionic or nonionic in character, or possibly amphoteric or zwitterionic. Cationic surfactant is possible if anionic is absent, but is not preferred. Soap may optionally be included, as well as non-soap surfactants.
  • One significant possibility is the use of a surfactant or mixture of surfactants of the above specified anionic and/or nonionic types, together with glycoside surfactants of the above specified type.
  • the amount of glycoside surfactant, anionic surfactant and/or ethoxylated fatty alcohol surfactant will be from 3 to 50% by weight of the composition. Desirably the total amount of surfactant lies in the same range. Preferred ranges, both for the specified surfactant and total surfactant are 3 to 30% by weight, more preferably, in the range from 5 or 10% to 25% by weight.
  • the cleaning compositions of this invention can contain all manner of detergent builders commonly taught for use in automatic dishwashing or other cleaning compositions.
  • the builders can include any of the conventional inorganic and organic water-soluble builder salts, also insoluble inorganic builders or mixtures thereof, and may comprise from 5 to 90% by weight of the detergent composition.
  • Typical of the well-known inorganic builders are the sodium and potassium salts of the following: pyrophosphate, tripolyphosphate, orthophosphate, carbonate, bicarbonate, sesquicarbonate and borate.
  • Other non-phosphorous salts including (insoluble) crystalline and amorphous aluminosilicates (e.g. zeolites) may be used as well.
  • Preferred builders can be selected from the group consisting of sodium tripolyphosphate, sodium carbonate, sodium bicarbonate and mixtures thereof. When present in these compositions, sodium tripolyphosphate concentrations will usually range from 2% to 40%, preferably from 5% to 30%. Sodium carbonate and bicarbonate, when present, can range from 10% to 50%, preferably from 20% to 40% by weight of the cleaning compositions. Potassium pyrophosphate is a preferred builder in gel formulations, where it may be used at from 3 to 30%, preferably from 10 to 20%.
  • Organic detergent builders can also be used in the present invention. They are generally sodium and potassium salts of the following: citrate, malonate or succinate substituted with a C8 to C24 alkyl group, nitrilotriacetates, phytates, polyphosponates, oxydisuccinates, oxydiacetates, carboxymethyloxy succinates, tetracarboxylates, starch, oxidized heteropolymeric polysaccharides, and polymeric polycarboxylates such as polyacrylates of molecular weight of from about 5,000 to about 200,000. Polyacetal carboxylates such as those described in U.S. Patent Nos. 4,144,226 and 4,146,495 may also be used.
  • Non-phosphate builders are particularly preferred for environmental reasons.
  • Sodium citrate is an especially preferred builder. When present, it is preferably used in an amount from about 1% to about 75% of the total weight of the detergent composition, especially 10 to 50% by weight.
  • detergent builders are meant to illustrate but not limit the types of builder that can be employed in the present invention.
  • compositions of this invention contain sodium or potassium silicate at a level of from about 1 to about 40% by weight of the cleaning composition, more preferably from 5 to 25%, even more preferably from 7 to 20%.
  • This material is employed as a cleaning ingredient, source of alkalinity, metal corrosion inhibitor and protector of glaze on china tableware.
  • the sodium or potassium silicate usuable herein will have a ratio of SiO2:Na2O or SiO2:K2O of from about 2.0 to about 3.2. Some of the silicate may be in solid form.
  • Useful is sodium silicate having a ratio of SiO2 : Na2O of higher than 2.0, preferably at least 2.4.
  • a composition contains less than 10% silicate, we prefer to include a zinc salt, such as zinc sulphate, especially if the composition dissolves to give an alkaline pH, e.g. pH over 8.5.
  • a zinc salt serves to protect glassware from attack by an alkaline wash liquor, and may suitably be used in amounts from 0.1 to 3% by weight.
  • compositions according to the present invention are free from chlorine bleach compounds but may contain a peroxygen bleach component. If present the amount will preferably lie in a range from 1 to 30% by weight.
  • a peroxygen bleach which may be employed is for example sodium perborate. This is preferably accompanied by a bleach activator which allows the liberation of active oxygen species at a lower temperature.
  • a preferred bleach activator is tetraacetyl ethylene diamine (TAED) but other activators for perborate are known and can be used.
  • the amounts of peroxygen bleach and bleach activator in an individual composition preferably do not exceed 20% and 15% by weight respectively.
  • peroxygen bleach is sodium percarbonate. Yet another is sodium monopersulphate. Further peroxygen bleaches which may be used are alkyl, alkenyl and aryl peroxy organic acids and their metal salts. Typical peroxy acids include
  • Thickeners are often desirable for liquid cleaning compositions.
  • Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite, saponite, and the like may be used to impart viscosity to liquid cleaning compositions.
  • Silica, silica gel, and aluminosilicate may also be used as thickeners.
  • Use of clay thickeners for automatic dishwashing compositions is disclosed, for example, in U.S. Patents Nos. 4,431,559; 4,511,487; 4,740,327; 4,752,409.
  • Use of salts of polymeric carboxylic acids is disclosed, for example, in UK Patent Application GB 2,164,350A.
  • bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP and H) ex English China Clay Co.
  • Polargel T is preferred as imparting a more intense white appearance to the composition than other clays.
  • polymers may be included. These may in particular assist in detergency building or be polymeric thickeners, which may be used alone or jointly with other types of thickeners. Notable are polymers containing carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potassium salts, the sodium salts being preferred. Preferred polymers are homopolymers and copolymers of acrylic acid and/or maleic acid or maleic anhydride. Of especial interest are polyacrylates, polyalphahydroxy acrylates, acrylic/maleic acid copolymers, and acrylic phosphinates. Other polymers which are especially preferred for use in liquid detergent compositions are deflocculating polymers such as for example disclosed in EP 346995.
  • the molecular weights of homopolymers and copolymers are generally 1000 to 150,000, preferably 1500 to 100,000.
  • Polyacylate thickeners may well have molecular weights from 300,000 up to 6 million.
  • the amount of any polymer may lie in the range from 0.5 to 5% or even 10% by weight of the composition.
  • a chlorine-stable polymeric thickener is particularly useful for liquid formulations with a "gel" appearance and rheology, particularly if a clear gel is desired.
  • U.S. Patent No. 4,260,528 discloses natural gums and resins for use in clear autodish detergents, which are not chlorine-stable.
  • Crosslinked acrylic acid polymers manufactured by B.F. Goodrich and sold under the trade name "Carbopol” have been found to be effective for production of clear gels, and Carbopol 940 having a molecular weight of about 4,000,000 is particularly preferred for maintaining high viscosity with excellent chlorine stability over extended periods.
  • Further suitable chlorine-stable polymeric thickeners are described in U.S. Patent 4,867,896.
  • the amount of thickener employed in the composition may range from 0 to 5%, preferably 1 to 3%.
  • Stabilizers and/or co-structurants such as long-chain calcium and sodium soaps and C12 to C18 alkyl sulphates are detailed in U.S. Patents Nos. 3,956,158 and 4,271,030 and the use of other metal salts of long-chain soaps is detailed in U.S. Patent No. 4,752,409.
  • the amount of stabilizer which may be used in the liquid cleaning compositions is from about 0.01 to about 5% by weight of the composition, preferably 0.1-2%. Such stabilizers are optional in gel formulations.
  • Co-structurants which are found especially suitable for gels include trivalent metal ions at 0.01-4% of the composition and/or water-soluble structuring chelants at 1-60%. These co-structurants are more fully described in EP-A-323209.
  • the agitation conditions in a dishwashing machine are more rigorous than those in a fabric washing machine and lead to foam formation.
  • Foam if it forms, can cause air to be drawn into the circulating pump. This can interfere with proper water circulation and the supply of water to the heating element. Excessive foam generation can eventually lead to air locking of the pump, which could wreck the machine by stopping the water supply to the heating element.
  • a composition of the invention may further include defoamer. Even if the cleaning composition has only low foaming surfactant, presence of a defoamer can assist to minimize foam which food soils can generate.
  • compositions contain a nonionic surfactant which includes ethylene oxide and propylene oxide residues. These surfactants have cloud points below the operating temperature and they therefore form hydrophobic droplets which exert an antifoam action.
  • Materials which may be utilised as defoamer in a composition of this invention include mono- and di- C8 to C22 alkyl phosphates and mineral oil/or wax. These may be used as a combination containing particles of the insoluble alkyl phosphate together with petroleum jelly. Possible alternatives to the alkyl phosphate include ethylene distearamide, calcium soap and finely divided silica, especially hydrophobed silica. Mineral oils and waxes which may be used include petroleum fractions, Fischer-Tropsch waxes, ozokerite, ceresin montan wax, beeswax, candelilla wax, camauba wax and mixtures thereof.
  • ketones of formula R7COR8 wherein R7 and R8 are both alkyl or alkenyl groups containing 8 to 24 carbon atoms and such that the ketone contains 25 to 49 carbon atoms.
  • Ketones of this type and their use as antifoam agents in (other) machine dishwashing compositions, are disclosed in EP-A-324339.
  • soap or fatty acid which becomes neutralised to soap in use of the composition.
  • Such soap or fatty acid should have an acyl group of 12 to 22 carbon atoms, especially 14 to 18 carbon atoms. If soap or fatty acid is used as defoamer some calcium salt may deliberately be included in the composition, thereby ensuring the presence of calcium ions to form a calcium soap which exerts the antifoaming action.
  • the composition may include 0.1 to 30% by weight of defoamer, preferably other than nonionic surfactant.
  • Non-soap defoamer may be used at levels towards the lower end of this range, e.g. 0.1 to 10%, preferably 0.5 to 2% or 5%.
  • Soap or fatty acid can be used as defoamer, and if present may be used in amounts from 0.1 to 30% by weight, especially 0.5 to 10%.
  • the surfactant is alkyl sulphate alone, it may be desirable to use a said ketone (in branched chain alcohol), soap or fatty acid as the defoamer and to avoid alkyl phosphates or mineral oil.
  • Minor amounts of various other components may be present in the cleaning composition. These include anti-scalants, corrosion-inhibitors anti-redeposition agents, anti-tarnish agents, other enzymes (especially amylase and/or lipase at 0.05-2% by weight, preferably 0.5-1.5%) and other functional additives and perfume.
  • compositions of this invention may take the form of a liquid or a gel.
  • the composition is preferably formulated to give a pH in the range 7 to 11, even better 8 to 11 if added to deionized water at a concentration of 2.0 grams/litre.
  • a particularly preferred pH is 9.0 to 9.5.
  • This example demonstrates action of removing soil from glass slides.
  • New glass slides, 5cm x 5cm were machine washed, repeatedly rinsed with demineralised water and soiled with about 55mg baked on egg-yolk per slide.
  • Results were as follows:- % Egg-yolk removal Wash Time (minutes) No enzyme No APG Enzyme only APG only APG+Enzyme 1 1.7 1.5 0.8 1.2 5 1.5 2.0 0.9 1.7 10 1.9 3.1 0.4 4.4 20 2.0 4.4 -0.2 15.2 30 2.4 5.8 0.2 22.4 40 2.6 8.1 -0.6 31.3 50 2.5 12.8 -1.1 48.1 60 2.6 20.1 -1.4 70.6
  • Example 2 The procedure was similar to Example 1. Several types of alkyl polyglycoside were employed. All solutions contained, per litre of water:- Sodium citrate dihydrate 0.60g Acrylic maleic copolymer 0.15g Sodium disilicate monohydrate 0.60g Alcalase 2.0T 30mg (giving activity 46 GU/ml of solution).
  • alkyl polyglycoside of general formula RO(G) x where G denotes a glucose residue and R is an alkyl chain.
  • the alkyl polyglycoside displayed various alkyl chain lengths R and various values of x, the degree of polymerisation.
  • Some solutions also contained:- 30mg Alcalase 2.OT (giving an activity of 46 GU/ml) and/or 0.5g ethyl 6-O-decanoyl glucoside
  • the solutions were used to wash glass slides stained with egg-yolk as in Example 1, or stainless steel slides stained with egg-yolk in the same way.
  • Results were as follows:- % Egg yolk removal from glass Wash time (minutes) enzyme only Glucoside only Enzyme + glucoside 10 4 ⁇ 1 2 ⁇ 1 4 ⁇ 1 20 9 ⁇ 0 0 ⁇ 1 17 ⁇ 8 30 15 ⁇ 1 1 ⁇ 1 34 ⁇ 11 40 27 ⁇ 3 1 ⁇ 1 53 ⁇ 17 % Egg yolk removal from stainless steel Wash time (minutes) enzyme only Glucoside only Enzyme + glucoside 10 4 ⁇ 0 2 ⁇ 0 4 ⁇ 0 20 8 ⁇ 1 2 ⁇ 0 9 ⁇ 8 30 16 ⁇ 1 2 ⁇ 1 34 ⁇ 7 40 25 ⁇ 4 2 ⁇ 0 54 ⁇ 11
  • a machine dishwashing formulation was a mixture containing: Amount by weight Percent by weight Na-citrate dihydrate 2.67g 18.5% Acrylic-maleic copolymer (Sokolan CP5) 0.67g 4.6% Na-disilicate monohydrate 2.67g 18.5% Oleic acid 3.44g 23.8% Ca-stearate 0.30g 2.1% Petroleum jelly 1.20g 8.3% APG 3.00g 20.7% Savinase 6.0CM (1544 GU/mg) 0.30g 2.1% Termamyl 6OT (4.8MU/mg) 0.20g 1.4%
  • the alkyl polyglycoside was of the formula RO(G) x where G denotes glucose, R is a C12-C14 alkyl chain and x averages 1.8.
  • This formulation was used to wash various stained glass slides using a Bosch S510 automatic dishwasher on its standard program and without salt added to the machine. The main wash temperature was 55°C, the final rinse temperature was 65°C. The water used tap water of 16° French Hardness.
  • the glass slides were stained with potato, a custard pudding or egg yolk.
  • the potato and custard pudding stains were aged at 30°C and 60% relative humidity for 16-24 hours.
  • the egg yolk stain was baked-on at 120°C for two hours. Removal of the stain was determined as loss in weight.
  • This example demonstrates synergistic action in removing soil from glass slides.
  • New glass slides, 5cm x 5cm were machine washed, repeatedly rinsed with demineralised water and soiled with about 55mg baked on egg-yolk per slide.
  • Results were as follows:- wt% Egg-yolk removal Wash Time (minutes) Enzyme only % SDS only % SDS+Enzyme % 10 1.3 -1.1 0.0 20 2.3 -1.0 6.5 30 2.1 -1.2 13.5 40 3.0 -3.3 23.8
  • Example 7 was repeated, using a larger amount of enzyme and a larger amount of a different anionic surfactant.
  • slides were removed from the wash solution they were replaced with a clean slide.
  • the washing solutions received: 30mg Alcalase 2.OT (providing 45 GU/ml in solution) and/or 0.5g of Texin ES68 which is a fatty acid ester sulphonate of formula in which R2 is derived from tallow and so is predominantly C16 and C18 alkyl and R3 is methyl.
  • Example 7 The procedure of Example 7 was repeated using SDS, and mixtures of SDS with equal weights of other surfactants. For each test the same total amount of surfactant (250mg/l) was used, and 20mg/l of Alcalase 2.OT was present.
  • Dobanol 91-6 is an ethoxylated fatty alcohol where the fatty alcohol has chain length 9 to 11 carbon atoms and the average degree of ethoxylation is 6. It has an HLB value of 12.5
  • Synperonic A7 is an ethoxylated fatty alcohol where the fatty alcohol has chain length 13 to 15 carbon atoms and the average number of ethylene oxide residues is 7. It has an HLB value of 12.2.
  • APG 300 is an alkyl polyglycoside of formula R5O(G) x where R5 is alkyl of 9 to 11 carbon atoms and x has average value of 1.4.
  • Example 7 was repeated using each of three nonionic surfactants in place of SDS.
  • the results expressed as wt% egg-yolk removal after 30 minutes, were: wt% egg-yolk removal Synperonic A3 + enzyme 15 ⁇ 3 Synperonic A7 + enzyme 33 ⁇ 6
  • Synperonic A3 is C13-C15 fatty alcohol ethoxylated with an average of 3 ethylene oxide residues. It has HLB value 7.9.
  • Synperonic A7 is, as mentioned in the last example, C13-C15 alcohol with an average of 7 ethylene oxide residues. HLB value is 12.2.
  • Dobanol 91-6 is a C9-C11 alcohol with an average of 6 ethylene oxide residues. HLB value is 12.5.
  • Example 7 was repeated twice using a larger amount of enzyme (as in Example 8) and two ethoxylated nonionic surfactants. In consequence the washing solutions received: 30mg Alcalase 2.OT (providing 45 GU/ml in solution) and/or 0.4g of either Synperonic A7 or Dobanol 91-6.
  • Example 7 was repeated using a larger amount of enzyme (as in Examples 8 and 11) and two anionic surfactants.
  • the washing solutions received: 30mg Alcalase 2.OT (providing 45 GU/ml in solution) and/or 250mg of either Empicol LX or 250 mg/litre of either sodium lauryl ether sulphate (LES) with average 3 ethylene oxide residues, or middle cut coconut alkyl sulphate (Empicol LX).
  • Termamyl is an amylase.
  • the formulations contained sodium dodecyl sulphate in amounts which were 0.75g, 1.5g and 3.0g.
  • Each formulation was used to wash various stained glass slides using a Bosch S510 automatic dishwasher on its standard program and without salt added to the machine.
  • the main wash temperature was 55°C
  • the final rinse temperature was 65°C.
  • the water used was tap water of 16° French Hardness.
  • the materials from which the various slides were made, the stains on them and the extent of removal are set out in the following table. In most instances the extent of removal was determined by weight loss. In a few instances the extent of removal was determined by visual inspection of the area which remains covered by the stain.
  • a composition containing Dehypon KE 2429 foam inhibitor (believed to be a mixture of branched chain alcohol and ketone according to EP-A-324,339) was used to wash a stainless steel plate 20cm x 6cm with almost 0.8g baked-on egg-yolk, in a Bosch 5510 machine.
  • the wash conditions were the same as for Example 12.
  • the composition contained: Sodium citrate dihydrate 5.0g Sodium dodecyl sulphate 1.25g Alcalase 2.OT 0.20g Dehypon KE2429 0.50g
  • Example 14 was repeated while also including 0.50g oleic acid in the composition.
  • proteases were includes in these formulations which were then used to wash porcelain and stainless steel slides stained with baked-on egg-yolk. The results, which are determined by loss in weight, are set out in the following table.

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EP19930200217 1992-02-03 1993-01-28 Waschmittelzusammensetzung Expired - Lifetime EP0554943B1 (de)

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Application Number Priority Date Filing Date Title
GB929202237A GB9202237D0 (en) 1992-02-03 1992-02-03 Detergent composition
GB9202237 1992-02-03
EP92302290 1992-03-17
EP92302290 1992-03-17

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EP0554943A2 true EP0554943A2 (de) 1993-08-11
EP0554943A3 EP0554943A3 (en) 1993-12-08
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014941A1 (en) * 1992-12-18 1994-07-07 Berol Nobel Ab Dishwasher detergent and use thereof
EP0634480A1 (de) * 1993-07-14 1995-01-18 The Procter & Gamble Company Reinigungsmittelzusammensetzungen
WO1996014374A1 (de) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Oberflächenaktive mittel enthaltend solubilisatoren
EP0755999A1 (de) * 1995-07-24 1997-01-29 The Procter & Gamble Company Waschmittelzusammensetzungen enthaltend eine spezifische Amylase und eine Protease
WO1997013832A1 (en) * 1995-10-06 1997-04-17 Unilever N.V. An anti-foam system based on hydrocarbon polymers and hydrophobic particulate solids
WO1997013833A1 (en) * 1995-10-06 1997-04-17 Unilever N.V. Anti-foam system for automatic dishwashing compositions
WO1998004239A3 (en) * 1996-07-25 1998-05-14 Procter & Gamble Shampoo compositions
WO1999023036A1 (de) * 1997-11-03 1999-05-14 Cognis Deutschland Gmbh Verfahren zur entfernung hydrophober verunreinigungen mittels spaltbarer nichtionischer tenside
EP0872541A3 (de) * 1997-04-16 1999-07-28 Henkel Kommanditgesellschaft auf Aktien Flüssige Feinwaschmittel in Mikroemulsionsform
WO2004111170A1 (en) * 2003-06-13 2004-12-23 Lamberti Spa Aqueous liquid detergent compositions comprising anionic esters of alkylpolyglycosides and enzymes
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
EP2428572A2 (de) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alpha-Amylase Varianten der Gattung Bacillus alcalophilus, Zusammensetzungen mit Alpha-Amylase Varianten und Anwendungsverfahren
WO2012123452A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2012123450A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirrspülmittel
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2838368B2 (ja) * 1994-07-22 1998-12-16 株式会社サンコンタクトレンズ コンタクトレンズ用の酵素洗浄液
US7271138B2 (en) * 2003-10-16 2007-09-18 The Procter & Gamble Company Compositions for protecting glassware from surface corrosion in automatic dishwashing appliances
KR101695483B1 (ko) * 2014-03-06 2017-01-13 (주)오성에버린 스프레이용 천연탈취제의 제조방법

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
DE2727463A1 (de) * 1976-06-24 1978-01-05 Procter & Gamble Reinigungsmittel, das insbesondere zur verwendung in geschirrspuelmaschinen geeignet ist
WO1986005187A1 (en) * 1985-03-07 1986-09-12 A.E. Staley Manufacturing Company Detergent composition containing an enzyme and a glycoside surfactant
GB8629537D0 (en) * 1986-12-10 1987-01-21 Unilever Plc Enzymatic dishwashing composition
GB2200132B (en) * 1986-12-15 1991-09-18 Colgate Palmolive Co Stabilised enzyme systems and compositions containing them
EP0342177B1 (de) * 1988-05-12 1995-07-12 The Procter & Gamble Company Flüssige Universalwaschmittel, welche anionische und nichtionische oberflächenaktive Mittel, Gerüststoffe und proteolytisches Enzym enthalten
EP0429124A1 (de) * 1989-11-21 1991-05-29 The Procter & Gamble Company Chlorfreie flüssige Zusammensetzungen für die automatische Geschirreinigung

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994014941A1 (en) * 1992-12-18 1994-07-07 Berol Nobel Ab Dishwasher detergent and use thereof
EP0634480A1 (de) * 1993-07-14 1995-01-18 The Procter & Gamble Company Reinigungsmittelzusammensetzungen
WO1996014374A1 (de) * 1994-11-02 1996-05-17 Henkel Kommanditgesellschaft Auf Aktien Oberflächenaktive mittel enthaltend solubilisatoren
EP0755999A1 (de) * 1995-07-24 1997-01-29 The Procter & Gamble Company Waschmittelzusammensetzungen enthaltend eine spezifische Amylase und eine Protease
EP0756000A1 (de) * 1995-07-24 1997-01-29 The Procter & Gamble Company Waschmittelzusammensetzungen enthaltend eine spezifische Amylase und lineares Alkylbenzolsulfonattensid
EP0756001A1 (de) * 1995-07-24 1997-01-29 The Procter & Gamble Company Waschmittelzusammensetzungen enthaltend eine spezifische Amylase une ein spezifisches oberflächenaktives System
WO1997013832A1 (en) * 1995-10-06 1997-04-17 Unilever N.V. An anti-foam system based on hydrocarbon polymers and hydrophobic particulate solids
WO1997013833A1 (en) * 1995-10-06 1997-04-17 Unilever N.V. Anti-foam system for automatic dishwashing compositions
US5695575A (en) * 1995-10-06 1997-12-09 Lever Brothers Company, Division Of Conopco, Inc. Anti-form system based on hydrocarbon polymers and hydrophobic particulate solids
US5705465A (en) * 1995-10-06 1998-01-06 Lever Brothers Company, Division Of Conopco, Inc. Anti-foam system for automatic dishwashing compositions
AU727942B2 (en) * 1995-10-06 2001-01-04 Unilever Plc Anti-foam system for automatic dishwashing compositions
WO1998004239A3 (en) * 1996-07-25 1998-05-14 Procter & Gamble Shampoo compositions
EP0872541A3 (de) * 1997-04-16 1999-07-28 Henkel Kommanditgesellschaft auf Aktien Flüssige Feinwaschmittel in Mikroemulsionsform
WO1999023036A1 (de) * 1997-11-03 1999-05-14 Cognis Deutschland Gmbh Verfahren zur entfernung hydrophober verunreinigungen mittels spaltbarer nichtionischer tenside
WO2004111170A1 (en) * 2003-06-13 2004-12-23 Lamberti Spa Aqueous liquid detergent compositions comprising anionic esters of alkylpolyglycosides and enzymes
EP2428572A2 (de) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alpha-Amylase Varianten der Gattung Bacillus alcalophilus, Zusammensetzungen mit Alpha-Amylase Varianten und Anwendungsverfahren
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
US8507243B2 (en) 2008-09-25 2013-08-13 Danisco Us Inc. Alpha-amylase blends and methods for using said blends
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
WO2012123452A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2012123450A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirrspülmittel

Also Published As

Publication number Publication date
EP0554943B1 (de) 1998-06-17
DE69319158T2 (de) 1998-10-29
JPH0830199B2 (ja) 1996-03-27
ES2118181T3 (es) 1998-09-16
DE69319158D1 (de) 1998-07-23
EP0554943A3 (en) 1993-12-08
NO930342D0 (no) 1993-02-01
JPH05271690A (ja) 1993-10-19
NO930342L (no) 1993-08-04
CA2088230A1 (en) 1993-08-04

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