EP0318204A1 - Machine dishwashing compositions - Google Patents

Machine dishwashing compositions Download PDF

Info

Publication number
EP0318204A1
EP0318204A1 EP88310845A EP88310845A EP0318204A1 EP 0318204 A1 EP0318204 A1 EP 0318204A1 EP 88310845 A EP88310845 A EP 88310845A EP 88310845 A EP88310845 A EP 88310845A EP 0318204 A1 EP0318204 A1 EP 0318204A1
Authority
EP
European Patent Office
Prior art keywords
tablet
tablets
composition
detergent
enzymes
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.)
Withdrawn
Application number
EP88310845A
Other languages
German (de)
French (fr)
Inventor
Jakob Van Dijk
Hidde Frankena
Hendrik Simon Kielman
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0318204A1 publication Critical patent/EP0318204A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609Protease or amylase in solid compositions only

Definitions

  • the present invention relates to machine dishwashing products in tablet form. More particularly it relates to tablet systems wherein incompatible ingredients are formulated into separate tablets, the tablets then being mixed to provide a product having all the desired ingredients.
  • the most common type of machine dishwashing cleanser is a powder or granulate.
  • the average particle size varies between approximately 0.05 and 2mm diameter.
  • the formulations usually contain alkali-metal polyphosphates, alkali-metal silicates, a bleach and a detergent.
  • the silicates usually sodium metasilicate, are hygroscopic, and consequently they are difficult to formulate into a spray-dried powder. Compositions are instead produced by a mixing and absorption technique.
  • the powder In use, the powder is dosed into a small dispenser in the dishwashing machine. During the washing cycle, it is flushed out by a water flow. However, due to the hygroscopicity, the powder can form lumps in the dispenser, resulting in low dosage into the wash. Anticaking ingredients such as paraffin have been added, but without complete success.
  • thixotropic liquids e.g. as described in GB 1 527 706 and GB 2 140 450.
  • the cleaning power of such compositions is not in general as good as conventional powder forms.
  • a third form of machine dishwashing product comprises tablets. Such forms have been disclosed in, e.g. FR 1 472 680, DE-OS-2 857 001 and DE-OS-3 315 950. These tablets may contain conventional ingredients. The disadvantages caused by caking and lump-formation can be substantially eliminated by production of a high relative mass solid tablet.
  • a detergent composition in tablet form comprising in combination at least two tablet types, incompatible components being distributed amongst said tablets such that no substantially incompatible ingredients are formulated within the same tablet type.
  • the basic composition of all the tablets may be the same. However, silicate components may be incorporated into half the tablets, enzyme components into the other half. Likewise, substantially incompatible ingredients such as bleaches and dyes could be kept separate. After manufacture, the tablets would be mixed to give a final product containing all the required ingredients.
  • the mixture of tablets generally a random mixture, may be filled directly from a package into the dishwashing machine cup dispenser.
  • compositions may contain one or more alkali salts commonly used in dishwashing compositions.
  • they may contain organic and/or inorganic builder salts such as alkali metal ortho-, pyro- and tripolyphosphates and hexametaphosphates, silicates, carbonates, borates, citrates, carboxymethyloxy-succinates, nitroloacetates and ethylenediaminetetra-acetates, polymeric polyelectrolytes such as polyacrylates, polymaleates and other known organic and inorganic builder compounds. Silicates and enzymes will usually be kept separate.
  • the total amount of alkali salts distributed throughout the tablets varies from 10-90% by weight, generally from 30-70% by weight.
  • compositions of the invention may also contain a detergent-active compound. If a detergent-active compound is included, it usually is in an amount of from 0.5-10%, usually 1-5%. Any well known type of detergent-active compound may be used, such as soaps, synthetic anionic, nonionic, amphoteric detergent surfactant and mixtures thereof. Preferably, a nonionic detergent surfactant is used, especially a low-foaming one. Suitable examples of such nonionic detergent surfactants can easily be found in M.Schick "Nonionic Surfactants" (1967).
  • the detergent-active compound may be present by itself in a single tablet type or in one or more tablet types having other components. Preferably the detergent-active compound is incorporated in each tablet type such that each tablet type has at least some detergent-active compound and one other component of the composition.
  • the tablet forms according to the present invention are of particular use in the formulation of enzymic detergents compositions.
  • enzymes proteolytic, amylolytic, lipolytic and cellulolytic enzymes can be used, as well as mixtures of such enzymes.
  • the enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferably they are of bacterial and fungal origin.
  • subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis , such as the commercially available Maxatase (R) (ex Gist-Brocades N.V., Delft, Holland) and Alcalase (R) (ex Novo Industri A/S, Copenhagen, Denmark).
  • R Maxatase
  • R Alcalase
  • proteases obtained from a strain of Bacillus having maximum activity in the pH range of 8-12, developed and sold by Novo Industri A/S under the registred trade-names Esperase (R) and Savinase (R) .
  • the preparation of such enzymes is described in British patent specification 1 243 784.
  • amylolytic enzymes are conmercially available amylases such as Maxamyl (R) (ex Gist-Brocades) and Termamyl (R) (ex Novo Industri A/S). Amylases as described in British patent specification 1 296 839 are also suitable.
  • Typical examples of commercial lipolytic enzymes are e.g. Lipase YL, Amano CE, Wallerstein AW, Lipase MY etc. and typical examples of cellulolytic enzymes are cellulases ex Humiscola insolens as described in German patent specification 3 117 250.
  • compositions of the invention preferably contain proteolytic and/or amylolytic enzymes, and especially preferably a mixture of proteolytic and amylolytic enzymes.
  • the amount of enzymes present in the composition is dictated by the enzymatic activity of the enzymes. The higher the activity, the lower the level of enzymes required in the composition. In general, the amount will vary between 0.001 and 10%, and for most practical purposes between 0.1 and 5% by total weight of the composition.
  • compositions may be formulated which also contain bleaching agents.
  • the amount of bleach may be 0.02 to 15% by weight.
  • Layered clays may be included within the tablets in order to reduce spot and film formation.
  • Suitable clays belong to the geological classes of the smectites, the kaolins, the illites, the attapulgites and the mixed layer clays. Particularly preferred are the hectorites, members of the smectite family.
  • the use of clays in machine dishwashing compositions is discussed in EP 0 139 329.
  • the clays may be present at from 0.01 to 60% by weight, preferably 0.5 to 25% by weight, most preferably 0.5 to 5% by weight of the total composition.
  • compositions may furthermore contain other useful additives such as, bleaching agent activators, enzyme-stabilising agents, hydrotropes, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and alkali metal or alkaline earth metal salts thereof, anti-corrosion agents such as fatty acids, benztriazole and so on, additionally, the compositions may contain filler materials; suitable fillers include alkali metal salts of sulphate and carbonate, and polymeric materials such as polyethylene glycol having molecular weight of 400-10,000.
  • compositions according to the present invention are particularly useful in forming coloured compositions, dyes often being unstable in the presence of bleaches or metasilicates.
  • Dyes may be formulated into separate tablets from incompatible components. Thus the end product would be, for example, green and white or red and white tablets.
  • the products of the present invention are formulated such that they provide a wash liquor with a pH of between 7 and 12, preferably between 9 and 11.
  • Hygroscopic materials may be coated with, e.g. water soluble resin coatings after pressing in order to prevent premature tablet decomposition.
  • the tablets may also incorporate effervescent compounds, such as sodium bicarbonate and citric acid. These compounds assist in dissolution of the tablets. It may also be desirable to incorporate materials which swell in contact with water, thus disrupting the tablet structure and increasing the rate of dissolution as the area in contact with the aqueous wash bath increases.
  • effervescent compounds such as sodium bicarbonate and citric acid. These compounds assist in dissolution of the tablets. It may also be desirable to incorporate materials which swell in contact with water, thus disrupting the tablet structure and increasing the rate of dissolution as the area in contact with the aqueous wash bath increases.
  • the tablets may contain from 0.2 to 40g of preformulation composition, preferably from 0.5 to 5g. They may be of various shapes, but are preferably cylindrical, about 1cm long and 0.5 cm diameter. These small sizes assist in solubility of the product.
  • the tablets may be made by any conventional process known in the art. They are generally made by pressing together finely divided powders of the individual components. Compaction pressures can range from 1 x 103 to 1 x 107 N m ⁇ 2, selection of a suitable pressure being made to produce a soluble tablet. Tablet densities may range from 0.5 to 2 g/ml. Conventional tabletting ingredients, such as gums, magnesium silicate and polyethylene glucol may be included within the compositions.
  • the tablets may be packaged after pressing into some suitable container. In general, a random mixture of tablet types will be mixed together. However, the proportions of the different tablets can be varied according to the amounts of different ingredients which are required. It could fall within the scope of the present invention that the tablet types are packaged separately, and added by the consumer to the wash. Thus, the detergent formulation can be tailored to the requirements of each wash.
  • a pack comprising a container and, packed thereinto, a first set of tablets comprising a synthetic organic detergent component and at least one other set of tablets comprising further detergent components, components being distributed amongst said tablet sets such that no substantially incompatible ingredients are within the same tablet set.
  • the invention further relates to a method of cleaning dishes which comprises admixing into a wash bath a plurality of tablets, the tablets being of differing types wherein substantially incompatible components are not within the same tablet type so as to produce an aqueous washing bath of dissolved detergent composition components.
  • Enzyme activity was measured as an integral of activity over a period of time.
  • Tablet combinations 1, 2 and 3 above were investigated, either crushed and added together as a powder, or added in tablet form.
  • Theoretical 100% activity 159. It is seen that at high metasilicate levels, integral enzyme activity is higher (i.e. higher activity for a longer period of time) when the detergent composition is added in the form of tablets rather than as a powder.

Abstract

A detergent composition adapted for machine dishwashing in tablet form comprising in combination at least two tablet types, incompatible components being distributed amongst said tablets such that no substantially incompatible ingredients are formulated within the same tablet type.

Description

  • The present invention relates to machine dishwashing products in tablet form. More particularly it relates to tablet systems wherein incompatible ingredients are formulated into separate tablets, the tablets then being mixed to provide a product having all the desired ingredients.
  • The most common type of machine dishwashing cleanser is a powder or granulate. The average particle size varies between approximately 0.05 and 2mm diameter. The formulations usually contain alkali-metal polyphosphates, alkali-metal silicates, a bleach and a detergent. The silicates, usually sodium metasilicate, are hygroscopic, and consequently they are difficult to formulate into a spray-dried powder. Compositions are instead produced by a mixing and absorption technique.
  • In use, the powder is dosed into a small dispenser in the dishwashing machine. During the washing cycle, it is flushed out by a water flow. However, due to the hygroscopicity, the powder can form lumps in the dispenser, resulting in low dosage into the wash. Anticaking ingredients such as paraffin have been added, but without complete success.
  • As a solution to the problem of caking and uneven dispensing, it has been proposed to use thixotropic liquids, e.g. as described in GB 1 527 706 and GB 2 140 450. However, the cleaning power of such compositions is not in general as good as conventional powder forms.
  • A third form of machine dishwashing product comprises tablets. Such forms have been disclosed in, e.g. FR 1 472 680, DE-OS-2 857 001 and DE-OS-3 315 950. These tablets may contain conventional ingredients. The disadvantages caused by caking and lump-formation can be substantially eliminated by production of a high relative mass solid tablet.
  • The formulation of high relative mass tablets does encounter other problems. For example, there are proposals to incorporate enzymes such as proteases and amylases into machine dishwashing compositions (e.g. GB 1 579 946). Enzymic mixtures have been shown to have a greater cleaning performance on soiled dishes and cookware. However, enzymes are not compatible with the hign pH resulting from incorporation of silicates that are usually included to build and to protect glazing.* Thus, the high pH's resulting from metasilicates have been shown to deactivate enzymes, particularly amylase. Furthermore, enzymes and bleaches often included to assist stain removal are incompatible. Solutions to the problem proposed include coating bleach components with soluble polymers such as methacrylates. Such treatments are very difficult when forming tablets.
  • There is therefore a need for a machine dish-washing composition which is free from such problems as caking and enzyme degradation and which will deliver a suitable cleaning ability.
  • Accordingly, there is now provided a detergent composition in tablet form comprising in combination at least two tablet types, incompatible components being distributed amongst said tablets such that no substantially incompatible ingredients are formulated within the same tablet type.
  • For example, the basic composition of all the tablets may be the same. However, silicate components may be incorporated into half the tablets, enzyme components into the other half. Likewise, substantially incompatible ingredients such as bleaches and dyes could be kept separate. After manufacture, the tablets would be mixed to give a final product containing all the required ingredients. The mixture of tablets, generally a random mixture, may be filled directly from a package into the dishwashing machine cup dispenser.
  • There is a surprising benefit which accompanies the formulation of the machine dishwashing compositions described below in the tablet form: i.e., the enzymes present in tablet formulations contribute substantially more activity than enzymes in powder. It is believed this benefit is due to the differing rates of tablet versus powder dissolution: the silicate component of the tablet composition dissolves more slowly than in powder, or at a rate relative to any buffering builder salts present which is slower than that in powders. In either case, the pH of the washing liquid would not rise as quickly to an enzyme-inactivating value as when a powder is used.
  • The dissolution rate of silicate with respect to buffering builder salts and/or enzymes seems to play an important role. This is because the first few minutes of a wash cycle using machine dishwash powder seems to inactivate a substantial amount of enzyme.
  • It is believed this phenomenon of improved enzyme activity from a dishwashing composition in tablet form may be further exploited. If the slower dissolution of silicate from a tablet relative to builder results in improved enzyme activity, then means for speeding up dissolution of builder may be incorporated in the tablet containing the builder. Such means are well known to the art and include incorporating in the tablet, an effervescent agent; an agent which expands upon contact with water; an agent which enhances water solubility of the tablet; or a mixture of such agents. Where one or more of these agents is incoporated in the tablet with the builder, the silicate is preferably in a tablet separate from the builder. Alternatively, one may choose to incorporate an agent in the tablet containing enzyme which delays dissolution. The purpose of this would be to prevent releasing the enzyme into the wash liquid at a time when the pH might be too high. It is clear that different combinations of the ingredients of the composition with one or more of such dissolution-accelerating or -decellerating agents may be made by a person of ordinary skill in the art.
  • The compositions may contain one or more alkali salts commonly used in dishwashing compositions. Thus, they may contain organic and/or inorganic builder salts such as alkali metal ortho-, pyro- and tripolyphosphates and hexametaphosphates, silicates, carbonates, borates, citrates, carboxymethyloxy-succinates, nitroloacetates and ethylenediaminetetra-acetates, polymeric polyelectrolytes such as polyacrylates, polymaleates and other known organic and inorganic builder compounds. Silicates and enzymes will usually be kept separate.
  • Usually, the total amount of alkali salts distributed throughout the tablets varies from 10-90% by weight, generally from 30-70% by weight.
  • The compositions of the invention may also contain a detergent-active compound. If a detergent-active compound is included, it usually is in an amount of from 0.5-10%, usually 1-5%. Any well known type of detergent-active compound may be used, such as soaps, synthetic anionic, nonionic, amphoteric detergent surfactant and mixtures thereof. Preferably, a nonionic detergent surfactant is used, especially a low-foaming one. Suitable examples of such nonionic detergent surfactants can easily be found in M.Schick "Nonionic Surfactants" (1967). The detergent-active compound may be present by itself in a single tablet type or in one or more tablet types having other components. Preferably the detergent-active compound is incorporated in each tablet type such that each tablet type has at least some detergent-active compound and one other component of the composition.
  • The tablet forms according to the present invention are of particular use in the formulation of enzymic detergents compositions. As enzymes, proteolytic, amylolytic, lipolytic and cellulolytic enzymes can be used, as well as mixtures of such enzymes. The enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferably they are of bacterial and fungal origin.
  • Suitabie examples of proteolytic enzymes are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available Maxatase (R) (ex Gist-Brocades N.V., Delft, Holland) and Alcalase (R) (ex Novo Industri A/S, Copenhagen, Denmark). Particularly suitable are proteases obtained from a strain of Bacillus having maximum activity in the pH range of 8-12, developed and sold by Novo Industri A/S under the registred trade-names Esperase (R) and Savinase (R). The preparation of such enzymes is described in British patent specification 1 243 784.
  • Suitable examples of amylolytic enzymes are conmercially available amylases such as Maxamyl (R) (ex Gist-Brocades) and Termamyl (R) (ex Novo Industri A/S). Amylases as described in British patent specification 1 296 839 are also suitable.
  • Typical examples of commercial lipolytic enzymes are e.g. Lipase YL, Amano CE, Wallerstein AW, Lipase MY etc. and typical examples of cellulolytic enzymes are cellulases ex Humiscola insolens as described in German patent specification 3 117 250.
  • The compositions of the invention preferably contain proteolytic and/or amylolytic enzymes, and especially preferably a mixture of proteolytic and amylolytic enzymes.
  • Usually the amount of enzymes present in the composition is dictated by the enzymatic activity of the enzymes. The higher the activity, the lower the level of enzymes required in the composition. In general, the amount will vary between 0.001 and 10%, and for most practical purposes between 0.1 and 5% by total weight of the composition.
  • According to the present invention, compositions may be formulated which also contain bleaching agents. The amount of bleach may be 0.02 to 15% by weight.
  • Layered clays may be included within the tablets in order to reduce spot and film formation. Suitable clays belong to the geological classes of the smectites, the kaolins, the illites, the attapulgites and the mixed layer clays. Particularly preferred are the hectorites, members of the smectite family. The use of clays in machine dishwashing compositions is discussed in EP 0 139 329. The clays may be present at from 0.01 to 60% by weight, preferably 0.5 to 25% by weight, most preferably 0.5 to 5% by weight of the total composition.
  • The compositions may furthermore contain other useful additives such as, bleaching agent activators, enzyme-stabilising agents, hydrotropes, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and alkali metal or alkaline earth metal salts thereof, anti-corrosion agents such as fatty acids, benztriazole and so on, additionally, the compositions may contain filler materials; suitable fillers include alkali metal salts of sulphate and carbonate, and polymeric materials such as polyethylene glycol having molecular weight of 400-10,000.
  • The compositions according to the present invention are particularly useful in forming coloured compositions, dyes often being unstable in the presence of bleaches or metasilicates. Dyes may be formulated into separate tablets from incompatible components. Thus the end product would be, for example, green and white or red and white tablets.
  • The products of the present invention are formulated such that they provide a wash liquor with a pH of between 7 and 12, preferably between 9 and 11.
  • Hygroscopic materials may be coated with, e.g. water soluble resin coatings after pressing in order to prevent premature tablet decomposition.
  • The tablets may also incorporate effervescent compounds, such as sodium bicarbonate and citric acid. These compounds assist in dissolution of the tablets. It may also be desirable to incorporate materials which swell in contact with water, thus disrupting the tablet structure and increasing the rate of dissolution as the area in contact with the aqueous wash bath increases.
  • The tablets may contain from 0.2 to 40g of preformulation composition, preferably from 0.5 to 5g. They may be of various shapes, but are preferably cylindrical, about 1cm long and 0.5 cm diameter. These small sizes assist in solubility of the product.
  • The tablets may be made by any conventional process known in the art. They are generally made by pressing together finely divided powders of the individual components. Compaction pressures can range from 1 x 10³ to 1 x 10⁷ N m⁻², selection of a suitable pressure being made to produce a soluble tablet. Tablet densities may range from 0.5 to 2 g/ml. Conventional tabletting ingredients, such as gums, magnesium silicate and polyethylene glucol may be included within the compositions.
  • The tablets may be packaged after pressing into some suitable container. In general, a random mixture of tablet types will be mixed together. However, the proportions of the different tablets can be varied according to the amounts of different ingredients which are required. It could fall within the scope of the present invention that the tablet types are packaged separately, and added by the consumer to the wash. Thus, the detergent formulation can be tailored to the requirements of each wash.
  • According to a further aspect of this invention there is provided a pack comprising a container and, packed thereinto, a first set of tablets comprising a synthetic organic detergent component and at least one other set of tablets comprising further detergent components, components being distributed amongst said tablet sets such that no substantially incompatible ingredients are within the same tablet set.
  • The invention further relates to a method of cleaning dishes which comprises admixing into a wash bath a plurality of tablets, the tablets being of differing types wherein substantially incompatible components are not within the same tablet type so as to produce an aqueous washing bath of dissolved detergent composition components.
  • The present invention will now be described in more detail with reference to the following non-limiting Example.
  • Example 1
  • The effect of sodium metasilicate on amylase activity was investigated.
  • Two powder compositions were formulated (X and Y)
    Figure imgb0001
  • Four tablet types were formulated: (A, B, C and D)
    Figure imgb0002
  • In combination, it will be seen;
    Figure imgb0003
  • Enzyme activity was measured as an integral of activity over a period of time.
  • Tablet combinations 1, 2 and 3 above were investigated, either crushed and added together as a powder, or added in tablet form.
    Figure imgb0004
  • Theoretical 100% activity = 159. It is seen that at high metasilicate levels, integral enzyme activity is higher (i.e. higher activity for a longer period of time) when the detergent composition is added in the form of tablets rather than as a powder.

Claims (7)

1. A detergent composition adapted for machine dishwashing in tablet form comprising in combination at least two tablet types, incompatible components being distributed amongst said tablets such that no substantially incompatible ingredients are formulated within the same tablet type.
2. A composition as claimed in claim 1 wherein enzymes and akali metal silicates are formulated into different tablets.
3. A composition as claimed in claim 1 or claim 2 comprising at least two tablet types, one tablet comprising an alkali-metal phosphate, an amylase and a protease and excluding a silicate and a bleach compound, the second tablet comprising an alkali-metal silicate and a bleach component and excluding enzymes.
4. A composition as claimed in claim 1 or claim 2 or claim 3 comprising at least two tablet types, each of these tablets incorporating a detergent-active compound.
5. A pack comprising a container and, packed thereinto, a first set of tablets comprising a synthetic organic detergent component and at least one other set of tablets comprising further detergent components, components being distributed amongst said tablet sets such that no substantially incompatible components are within the same tablet set.
6. A method of washing dishes in a machine dishwasher comprising forming a wash bath by mixing the detergent composition in tablet form of claim 1 with water, contacting soiled plates with the wash bath, and rinsing the wash bath from the plates.
7. A machine dishwashing composition in tablet form substantially as described herein.
EP88310845A 1987-11-19 1988-11-17 Machine dishwashing compositions Withdrawn EP0318204A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB878727135A GB8727135D0 (en) 1987-11-19 1987-11-19 Machine dishwashing composition
GB8727135 1987-11-19

Publications (1)

Publication Number Publication Date
EP0318204A1 true EP0318204A1 (en) 1989-05-31

Family

ID=10627237

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88310845A Withdrawn EP0318204A1 (en) 1987-11-19 1988-11-17 Machine dishwashing compositions

Country Status (7)

Country Link
EP (1) EP0318204A1 (en)
JP (1) JPH02501489A (en)
AU (1) AU2562488A (en)
BR (1) BR8807311A (en)
GB (1) GB8727135D0 (en)
WO (1) WO1989004863A1 (en)
ZA (1) ZA888565B (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466485A2 (en) * 1990-07-13 1992-01-15 Unilever Plc Detergent compositions
EP0481547A1 (en) * 1990-10-17 1992-04-22 Unilever N.V. Machine dishwashing detergent tablets
WO1993005135A1 (en) * 1991-08-29 1993-03-18 Henkel Kommanditgesellschaft Auf Aktien Use of strongly alkaline agents to prevent silver cutlery from tarnishing in washing-up machines
DE4219620A1 (en) * 1992-06-16 1993-12-23 Licentia Gmbh Domestic dishwasher detergent feed - has separate and time displaced feeds of different media to the washing water
WO1996016152A1 (en) * 1994-11-24 1996-05-30 Unilever N.V. A detergent composition and method for warewashing
US5658874A (en) * 1994-11-14 1997-08-19 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent tablet compositions
US5916866A (en) * 1994-11-14 1999-06-29 Lever Brothers Company, Division Of Conopco, Inc. Preparation of laundry detergent tablets
DE19845602A1 (en) * 1998-10-05 2000-04-06 Henkel Kgaa Detergent tab pack for dishwashers
WO2000050557A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Washing and cleaning agent shaped bodies which are stable in storage
WO2000065021A1 (en) * 1999-04-23 2000-11-02 Henkel Kommanditgesellschaft Auf Aktien Detergent tablets with an improved performance for dishwashing machines
WO2001059058A1 (en) * 2000-02-09 2001-08-16 Reckitt Benckiser N.V. Detergent composition in tablet form
WO2001059056A1 (en) * 2000-02-09 2001-08-16 Reckitt Benckiser N.V. Detergent composition in tablet form
WO2002016540A1 (en) * 2000-08-21 2002-02-28 Clariant Finance (Bvi) Limited Enzyme compositions in tablet form
WO2007007034A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Cleaning article and cleaning method
WO2007007032A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
WO2007007037A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
WO2007007030A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
EP2199386A1 (en) 1993-10-08 2010-06-23 Novozymes A/S Amylase variants
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide
EP2428572A2 (en) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alkaliphilic Bacillus species alpha-amylase variants, compositions comprising alpha-amylase variants, and methods of use
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
US8814862B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9022724D0 (en) * 1990-10-19 1990-12-05 Unilever Plc Detergent compositions
GB9802390D0 (en) 1998-02-04 1998-04-01 Unilever Plc Detergent compositions
JP2017008267A (en) * 2015-06-25 2017-01-12 株式会社ニイタカ Cartridge detergent
JP6695103B2 (en) * 2015-06-25 2020-05-20 株式会社ニイタカ Cartridge cleaning agent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH421411A (en) * 1963-04-08 1966-09-30 Unilever Nv Process for cleaning tableware in machines, e.g. B. Dishwashers
DE1803099A1 (en) * 1967-10-16 1969-05-14 Unilever Nv Enzyme-containing detergents and cleaning agents
DE2030060A1 (en) * 1969-06-18 1971-02-04 Purodor S A Laboratoires de Chimie Appliquee, Paris Products for the maintenance, deodorization and cleaning of sanitary installations and processes for their manufacture
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH421411A (en) * 1963-04-08 1966-09-30 Unilever Nv Process for cleaning tableware in machines, e.g. B. Dishwashers
DE1803099A1 (en) * 1967-10-16 1969-05-14 Unilever Nv Enzyme-containing detergents and cleaning agents
DE2030060A1 (en) * 1969-06-18 1971-02-04 Purodor S A Laboratoires de Chimie Appliquee, Paris Products for the maintenance, deodorization and cleaning of sanitary installations and processes for their manufacture
US4099912A (en) * 1974-05-15 1978-07-11 Colgate-Palmolive Company Detergent compositions and washing methods including and utilizing separate tablets of components

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466485A3 (en) * 1990-07-13 1992-03-04 Unilever Plc Detergent compositions
US5225100A (en) * 1990-07-13 1993-07-06 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
EP0466485A2 (en) * 1990-07-13 1992-01-15 Unilever Plc Detergent compositions
EP0481547A1 (en) * 1990-10-17 1992-04-22 Unilever N.V. Machine dishwashing detergent tablets
WO1993005135A1 (en) * 1991-08-29 1993-03-18 Henkel Kommanditgesellschaft Auf Aktien Use of strongly alkaline agents to prevent silver cutlery from tarnishing in washing-up machines
DE4219620A1 (en) * 1992-06-16 1993-12-23 Licentia Gmbh Domestic dishwasher detergent feed - has separate and time displaced feeds of different media to the washing water
EP2199386A1 (en) 1993-10-08 2010-06-23 Novozymes A/S Amylase variants
US5658874A (en) * 1994-11-14 1997-08-19 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent tablet compositions
US5916866A (en) * 1994-11-14 1999-06-29 Lever Brothers Company, Division Of Conopco, Inc. Preparation of laundry detergent tablets
WO1996016152A1 (en) * 1994-11-24 1996-05-30 Unilever N.V. A detergent composition and method for warewashing
US5807438A (en) * 1994-11-24 1998-09-15 Diversey Lever, Inc. Detergent composition and method for warewashing
AU702654B2 (en) * 1994-11-24 1999-02-25 Johnsondiversey, Inc. A detergent composition and method for warewashing
US6610643B1 (en) 1998-10-05 2003-08-26 Henkel Kommanditgesellschaft Auf Aktien Detergent tablet packaging for dishwashers
DE19845602A1 (en) * 1998-10-05 2000-04-06 Henkel Kgaa Detergent tab pack for dishwashers
WO2000050557A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Washing and cleaning agent shaped bodies which are stable in storage
WO2000065021A1 (en) * 1999-04-23 2000-11-02 Henkel Kommanditgesellschaft Auf Aktien Detergent tablets with an improved performance for dishwashing machines
WO2001059058A1 (en) * 2000-02-09 2001-08-16 Reckitt Benckiser N.V. Detergent composition in tablet form
WO2001059056A1 (en) * 2000-02-09 2001-08-16 Reckitt Benckiser N.V. Detergent composition in tablet form
GB2361240A (en) * 2000-02-09 2001-10-17 Reckitt Benckiser Nv Low mass detergent tablet
WO2002016540A1 (en) * 2000-08-21 2002-02-28 Clariant Finance (Bvi) Limited Enzyme compositions in tablet form
US11246645B2 (en) 2005-05-12 2022-02-15 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US10463420B2 (en) 2005-05-12 2019-11-05 Innovatech Llc Electrosurgical electrode and method of manufacturing same
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US8814863B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US8814862B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
WO2007007032A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
GB2428244A (en) * 2005-07-08 2007-01-24 Reckitt Benckiser Nv Reduced mass cleaning tablet for ware-washing
GB2428247A (en) * 2005-07-08 2007-01-24 Reckitt Benckiser Nv Reduced mass detergent tablet and packaging
WO2007007034A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Cleaning article and cleaning method
GB2428245A (en) * 2005-07-08 2007-01-24 Reckitt Benckiser Nv Reduced mass detergent tablets
WO2007007037A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
WO2007007030A1 (en) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article and method
GB2428248A (en) * 2005-07-08 2007-01-24 Reckitt Benckiser Nv Reduced mass detergent tablets
EP2428572A2 (en) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Alkaliphilic Bacillus species alpha-amylase variants, compositions comprising alpha-amylase variants, and methods of use
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
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
WO2011049945A2 (en) 2009-10-23 2011-04-28 Danisco Us Inc. Methods for reducing blue saccharide

Also Published As

Publication number Publication date
ZA888565B (en) 1990-07-25
AU2562488A (en) 1989-05-25
GB8727135D0 (en) 1987-12-23
WO1989004863A1 (en) 1989-06-01
BR8807311A (en) 1990-03-01
JPH02501489A (en) 1990-05-24

Similar Documents

Publication Publication Date Title
EP0318204A1 (en) Machine dishwashing compositions
EP0139329B1 (en) Dishwashing compositions
EP0741776B2 (en) Process for the preparation of detergent tablets
US5133892A (en) Machine dishwashing detergent tablets
EP1741774B1 (en) Machine dishwashing compositions and their use
US6228825B1 (en) Automatic dishwashing cleaning system
US3798181A (en) Enzymatic detergent bar
EP0533239B1 (en) Aqueous liquid cleaning compositions
JPS6037160B2 (en) packaged detergent composition
US5719112A (en) Dishwashing composition
CA2165155C (en) Concentrated nil-phosphate liquid automatic dishwashing detergent compositions containing enzyme
US5240632A (en) Machine dishwasher water spot control composition
CA1334389C (en) Machine dishwasher water spot control composition
US5112518A (en) Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US5527483A (en) Nonaqueous gelled automatic dishwashing composition containing enzymes
JPH02504649A (en) Enzyme composition for washing and rinsing dishes
EP0561446B1 (en) Detergent compositions
US6410500B1 (en) Moulded body dishwasher detergents with soil release polymers
US5510048A (en) Nonaqueous liquid, phosphate-free, improved autoamatic dishwashing composition containing enzymes
CA2300643A1 (en) Dishwasher detergent shaped bodies containing surfactants
AU2011225893A1 (en) Detergent composition
US5545344A (en) Nonaqueous liquid, improved automatic dishwashing composition containing enzymes
EP0339707A2 (en) Encapsulated liquid detergent composition
CA2298283A1 (en) Dishwasher detergent shaped bodies containing soil-release polymers
US5618465A (en) Nonaqueous liquid automatic dishwashing composition containing 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): CH DE ES FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19890612

17Q First examination report despatched

Effective date: 19900903

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19910115