EP0318204A1 - Compositions pour le lavage en machine de la vaisselle - Google Patents

Compositions pour le lavage en machine de la vaisselle Download PDF

Info

Publication number: EP0318204A1
Authority: EP; European Patent Office
Prior art keywords: tablet; tablets; composition; detergent; enzymes
Prior art date: 1987-11-19
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 Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn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)

English (en)

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.)

1987-11-19

Filing date

1988-11-17

Publication date

1989-05-31

1988-11-17 Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC

1989-05-31 Publication of EP0318204A1 publication Critical patent/EP0318204A1/fr

Status Withdrawn legal-status Critical Current

Links

239000000203 mixture Substances 0.000 title claims abstract description 51
238000004851 dishwashing Methods 0.000 title claims abstract description 16
239000003599 detergent Substances 0.000 claims abstract description 16
239000004615 ingredient Substances 0.000 claims abstract description 13
102000004190 Enzymes Human genes 0.000 claims description 32
108090000790 Enzymes Proteins 0.000 claims description 32
150000001875 compounds Chemical class 0.000 claims description 11
239000007844 bleaching agent Substances 0.000 claims description 7
108010065511 Amylases Proteins 0.000 claims description 6
102000013142 Amylases Human genes 0.000 claims description 6
BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
235000019418 amylase Nutrition 0.000 claims description 6
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
108091005804 Peptidases Proteins 0.000 claims description 4
238000000034 method Methods 0.000 claims description 4
239000004382 Amylase Substances 0.000 claims description 3
239000004365 Protease Substances 0.000 claims description 3
229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
238000002156 mixing Methods 0.000 claims description 2
102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 1
229910000318 alkali metal phosphate Inorganic materials 0.000 claims 1
229910052914 metal silicate Inorganic materials 0.000 claims 1
239000003826 tablet Substances 0.000 description 58
229940088598 enzyme Drugs 0.000 description 30
239000000843 powder Substances 0.000 description 15
230000000694 effects Effects 0.000 description 12
239000003795 chemical substances by application Substances 0.000 description 8
238000004090 dissolution Methods 0.000 description 7
-1 alkali metal ortho- Chemical class 0.000 description 5
238000009472 formulation Methods 0.000 description 5
239000000047 product Substances 0.000 description 5
229910052783 alkali metal Inorganic materials 0.000 description 4
230000003625 amylolytic effect Effects 0.000 description 4
238000004140 cleaning Methods 0.000 description 4
239000000463 material Substances 0.000 description 4
150000004760 silicates Chemical class 0.000 description 4
102000035195 Peptidases Human genes 0.000 description 3
108010056079 Subtilisins Proteins 0.000 description 3
102000005158 Subtilisins Human genes 0.000 description 3
150000001340 alkali metals Chemical class 0.000 description 3
229940025131 amylases Drugs 0.000 description 3
KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
239000000975 dye Substances 0.000 description 3
239000007788 liquid Substances 0.000 description 3
238000003825 pressing Methods 0.000 description 3
230000002797 proteolythic effect Effects 0.000 description 3
150000003839 salts Chemical class 0.000 description 3
239000004094 surface-active agent Substances 0.000 description 3
238000005406 washing Methods 0.000 description 3
239000004367 Lipase Substances 0.000 description 2
102000004882 Lipase Human genes 0.000 description 2
108090001060 Lipase Proteins 0.000 description 2
239000004115 Sodium Silicate Substances 0.000 description 2
UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
150000001447 alkali salts Chemical class 0.000 description 2
230000001580 bacterial effect Effects 0.000 description 2
230000003139 buffering effect Effects 0.000 description 2
238000000576 coating method Methods 0.000 description 2
230000001461 cytolytic effect Effects 0.000 description 2
239000000945 filler Substances 0.000 description 2
230000002538 fungal effect Effects 0.000 description 2
235000019421 lipase Nutrition 0.000 description 2
230000002366 lipolytic effect Effects 0.000 description 2
238000004519 manufacturing process Methods 0.000 description 2
235000019795 sodium metasilicate Nutrition 0.000 description 2
229910052911 sodium silicate Inorganic materials 0.000 description 2
NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
239000007916 tablet composition Substances 0.000 description 2
CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
241000193830 Bacillus <bacterium> Species 0.000 description 1
241000194108 Bacillus licheniformis Species 0.000 description 1
235000014469 Bacillus subtilis Nutrition 0.000 description 1
BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical class [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
102000005575 Cellulases Human genes 0.000 description 1
108010084185 Cellulases Proteins 0.000 description 1
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
239000004150 EU approved colour Substances 0.000 description 1
239000004698 Polyethylene Substances 0.000 description 1
239000002202 Polyethylene glycol Substances 0.000 description 1
229920000388 Polyphosphate Polymers 0.000 description 1
240000004808 Saccharomyces cerevisiae Species 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical class [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
238000010521 absorption reaction Methods 0.000 description 1
239000002253 acid Substances 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
239000012190 activator Substances 0.000 description 1
239000000654 additive Substances 0.000 description 1
229910052784 alkaline earth metal Inorganic materials 0.000 description 1
235000012211 aluminium silicate Nutrition 0.000 description 1
125000000129 anionic group Chemical group 0.000 description 1
238000010936 aqueous wash Methods 0.000 description 1
QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
150000001642 boronic acid derivatives Chemical class 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
230000015556 catabolic process Effects 0.000 description 1
239000007795 chemical reaction product Substances 0.000 description 1
150000001860 citric acid derivatives Chemical class 0.000 description 1
239000011248 coating agent Substances 0.000 description 1
238000005056 compaction Methods 0.000 description 1
238000005260 corrosion Methods 0.000 description 1
238000000354 decomposition reaction Methods 0.000 description 1
238000006731 degradation reaction Methods 0.000 description 1
230000001934 delay Effects 0.000 description 1
235000014113 dietary fatty acids Nutrition 0.000 description 1
230000002255 enzymatic effect Effects 0.000 description 1
239000000194 fatty acid Substances 0.000 description 1
229930195729 fatty acid Natural products 0.000 description 1
150000004665 fatty acids Chemical class 0.000 description 1
239000012467 final product Substances 0.000 description 1
238000005187 foaming Methods 0.000 description 1
230000002070 germicidal effect Effects 0.000 description 1
239000008187 granular material Substances 0.000 description 1
239000003752 hydrotrope Substances 0.000 description 1
238000010348 incorporation Methods 0.000 description 1
HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
239000000391 magnesium silicate Substances 0.000 description 1
229910052919 magnesium silicate Inorganic materials 0.000 description 1
235000019792 magnesium silicate Nutrition 0.000 description 1
108010003855 mesentericopeptidase Proteins 0.000 description 1
150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
108010020132 microbial serine proteinases Proteins 0.000 description 1
239000002736 nonionic surfactant Substances 0.000 description 1
229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
239000012188 paraffin wax Substances 0.000 description 1
239000002245 particle Substances 0.000 description 1
239000002304 perfume Substances 0.000 description 1
229920000058 polyacrylate Polymers 0.000 description 1
229920000867 polyelectrolyte Polymers 0.000 description 1
229920000573 polyethylene Polymers 0.000 description 1
229920001223 polyethylene glycol Polymers 0.000 description 1
229920000642 polymer Polymers 0.000 description 1
239000001205 polyphosphate Substances 0.000 description 1
235000011176 polyphosphates Nutrition 0.000 description 1
230000002028 premature Effects 0.000 description 1
238000002360 preparation method Methods 0.000 description 1
229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 1
239000011347 resin Substances 0.000 description 1
229920005989 resin Polymers 0.000 description 1
229910021647 smectite Inorganic materials 0.000 description 1
239000000344 soap Substances 0.000 description 1
229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
235000017557 sodium bicarbonate Nutrition 0.000 description 1
235000019832 sodium triphosphate Nutrition 0.000 description 1
239000007787 solid Substances 0.000 description 1
239000007944 soluble tablet Substances 0.000 description 1
239000003381 stabilizer Substances 0.000 description 1
229910021653 sulphate ion Inorganic materials 0.000 description 1
239000000375 suspending agent Substances 0.000 description 1
108010075550 termamyl Proteins 0.000 description 1
230000009974 thixotropic effect Effects 0.000 description 1
238000011282 treatment Methods 0.000 description 1
235000013311 vegetables Nutrition 0.000 description 1

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
- C11D3/3942—Inorganic per-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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
- 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
- C11D3/38609—Protease 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.

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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)
Investigating Or Analyzing Materials By The Use Of Ultrasonic Waves (AREA)
Ultra Sonic Daignosis Equipment (AREA)
Transducers For Ultrasonic Waves (AREA)

EP88310845A 1987-11-19 1988-11-17 Compositions pour le lavage en machine de la vaisselle Withdrawn EP0318204A1 (fr)

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 (fr)	1989-05-31

Family

ID=10627237

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP88310845A Withdrawn EP0318204A1 (fr)	1987-11-19	1988-11-17	Compositions pour le lavage en machine de la vaisselle

Country Status (7)

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

Cited By (26)

* 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
EP0481547A1 (fr) *	1990-10-17	1992-04-22	Unilever N.V.	Comprimés détergents pour le lavage de la vaisselle en machine
WO1993005135A1 (fr) *	1991-08-29	1993-03-18	Henkel Kommanditgesellschaft Auf Aktien	Utilisation de produits fortement alcalins pour eviter le ternissement de couverts en argent dans des lave-vaisselle
DE4219620A1 (de) *	1992-06-16	1993-12-23	Licentia Gmbh	Verfahren zur Reinigungsmittelzugabe bei Haushalt-Geschirrspülmaschinen
WO1996016152A1 (fr) *	1994-11-24	1996-05-30	Unilever N.V.	Composition de detergent et procede de lavage de vaisselle
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 (de) *	1998-10-05	2000-04-06	Henkel Kgaa	Spülmittel-Tab-Packung für Geschirrspülmaschinen
WO2000050557A1 (fr) *	1999-02-25	2000-08-31	Henkel Kommanditgesellschaft Auf Aktien	Corps moules de produits de lavage et de nettoyage stables au stockage
WO2000065021A1 (fr) *	1999-04-23	2000-11-02	Henkel Kommanditgesellschaft Auf Aktien	Comprimes d'agents de nettoyage a performance ameliorees pour le lavage de la vaisselle en machine
WO2001059056A1 (fr) *	2000-02-09	2001-08-16	Reckitt Benckiser N.V.	Composition detergente sous forme de comprimes
WO2001059058A1 (fr) *	2000-02-09	2001-08-16	Reckitt Benckiser N.V.	Composition detergente sous forme de pastille
WO2002016540A1 (fr) *	2000-08-21	2002-02-28	Clariant Finance (Bvi) Limited	Compositions enzymatiques sous forme de pastilles
WO2007007030A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
WO2007007032A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
WO2007007037A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
WO2007007034A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article de nettoyage et procédé de nettoyage
EP2199386A1 (fr)	1993-10-08	2010-06-23	Novozymes A/S	Variants d'amylase
WO2011049945A2 (fr)	2009-10-23	2011-04-28	Danisco Us Inc.	Procédés destinés à réduire le saccharide donnant une couleur bleue
EP2428572A2 (fr)	2007-03-09	2012-03-14	Danisco US, Inc., Genencor Division	Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
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
US8814863B2 (en)	2005-05-12	2014-08-26	Innovatech, Llc	Electrosurgical electrode and method of manufacturing same
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
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
JP6695103B2 (ja) *	2015-06-25	2020-05-20	株式会社ニイタカ	カートリッジ洗浄剤
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US5225100A (en) *	1990-07-13	1993-07-06	Lever Brothers Company, Division Of Conopco, Inc.	Detergent compositions
EP0466485A3 (en) *	1990-07-13	1992-03-04	Unilever Plc	Detergent compositions
EP0481547A1 (fr) *	1990-10-17	1992-04-22	Unilever N.V.	Comprimés détergents pour le lavage de la vaisselle en machine
WO1993005135A1 (fr) *	1991-08-29	1993-03-18	Henkel Kommanditgesellschaft Auf Aktien	Utilisation de produits fortement alcalins pour eviter le ternissement de couverts en argent dans des lave-vaisselle
DE4219620A1 (de) *	1992-06-16	1993-12-23	Licentia Gmbh	Verfahren zur Reinigungsmittelzugabe bei Haushalt-Geschirrspülmaschinen
EP2199386A1 (fr)	1993-10-08	2010-06-23	Novozymes A/S	Variants d'amylase
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
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
WO1996016152A1 (fr) *	1994-11-24	1996-05-30	Unilever N.V.	Composition de detergent et procede de lavage de vaisselle
DE19845602A1 (de) *	1998-10-05	2000-04-06	Henkel Kgaa	Spülmittel-Tab-Packung für Geschirrspülmaschinen
US6610643B1 (en)	1998-10-05	2003-08-26	Henkel Kommanditgesellschaft Auf Aktien	Detergent tablet packaging for dishwashers
WO2000050557A1 (fr) *	1999-02-25	2000-08-31	Henkel Kommanditgesellschaft Auf Aktien	Corps moules de produits de lavage et de nettoyage stables au stockage
WO2000065021A1 (fr) *	1999-04-23	2000-11-02	Henkel Kommanditgesellschaft Auf Aktien	Comprimes d'agents de nettoyage a performance ameliorees pour le lavage de la vaisselle en machine
GB2361240A (en) *	2000-02-09	2001-10-17	Reckitt Benckiser Nv	Low mass detergent tablet
WO2001059058A1 (fr) *	2000-02-09	2001-08-16	Reckitt Benckiser N.V.	Composition detergente sous forme de pastille
WO2001059056A1 (fr) *	2000-02-09	2001-08-16	Reckitt Benckiser N.V.	Composition detergente sous forme de comprimes
WO2002016540A1 (fr) *	2000-08-21	2002-02-28	Clariant Finance (Bvi) Limited	Compositions enzymatiques sous forme de pastilles
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
US8814862B2 (en)	2005-05-12	2014-08-26	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
WO2007007037A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
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WO2007007030A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
GB2428244A (en) *	2005-07-08	2007-01-24	Reckitt Benckiser Nv	Reduced mass cleaning tablet for ware-washing
WO2007007032A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article et procédé
WO2007007034A1 (fr) *	2005-07-08	2007-01-18	Reckitt Benckiser N.V.	Article de nettoyage et procédé de nettoyage
GB2428247A (en) *	2005-07-08	2007-01-24	Reckitt Benckiser Nv	Reduced mass detergent tablet and packaging
EP2428572A2 (fr)	2007-03-09	2012-03-14	Danisco US, Inc., Genencor Division	Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
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
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 (fr)	2009-10-23	2011-04-28	Danisco Us Inc.	Procédés destinés à réduire le saccharide donnant une couleur bleue

Also Published As

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

Legal Events

Date	Code	Title	Description
1989-04-15	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
1989-05-31	AK	Designated contracting states	Kind code of ref document: A1 Designated state(s): CH DE ES FR GB IT LI NL SE
1989-08-09	17P	Request for examination filed	Effective date: 19890612
1990-10-17	17Q	First examination report despatched	Effective date: 19900903
1991-06-10	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
1991-07-31	18D	Application deemed to be withdrawn	Effective date: 19910115

Publication	Publication Date	Title
EP0318204A1 (fr)	1989-05-31	Compositions pour le lavage en machine de la vaisselle
EP0139329B1 (fr)	1990-03-14	Compositions pour laver la vaisselle
EP0741776B2 (fr)	2001-10-24	Procede de preparation de pastilles detergentes
US5133892A (en)	1992-07-28	Machine dishwashing detergent tablets
EP1741774B1 (fr)	2008-08-06	Compositions pour lave-vaisselle automatique et leur utilisation
EP0533239B1 (fr)	1998-04-01	Compositions détergentes aqueuses et liquides
EP2245129B1 (fr)	2012-05-09	Compositions de détergent pour machine à laver la vaisselle
US6228825B1 (en)	2001-05-08	Automatic dishwashing cleaning system
US3798181A (en)	1974-03-19	Enzymatic detergent bar
JPS6037160B2 (ja)	1985-08-24	包装された洗剤組成物
US5719112A (en)	1998-02-17	Dishwashing composition
CA2165155C (fr)	1999-06-29	Compositions detergentes liquides concentrees, sans phosphate, mais avec enzymes, pour lave-vaisselle
US5112518A (en)	1992-05-12	Enzymatic dishwashing composition containing a chlorine-type bleaching agent
US5240632A (en)	1993-08-31	Machine dishwasher water spot control composition
CA1334389C (fr)	1995-02-14	Composition anti-taches pour lave-vaisselle
JPH02504649A (ja)	1990-12-27	皿を洗いすすぐための酵素組成物
US5527483A (en)	1996-06-18	Nonaqueous gelled automatic dishwashing composition containing enzymes
NZ242843A (en)	1995-03-28	Nonaqueous liquid dishwashing composition comprising protease & amylase enzymes
EP0561446B1 (fr)	1998-07-15	Compositions détergentes
US5510048A (en)	1996-04-23	Nonaqueous liquid, phosphate-free, improved autoamatic dishwashing composition containing enzymes
CA2300643A1 (fr)	2000-05-29	Objets sous forme de detergent pour lave-vaisselle contenant des surfactants
US6410500B1 (en)	2002-06-25	Moulded body dishwasher detergents with soil release polymers
US5545344A (en)	1996-08-13	Nonaqueous liquid, improved automatic dishwashing composition containing enzymes
NZ250780A (en)	1995-04-27	Enzyme-containing, gelled, automatic dishwashing detergent composition
EP0339707A2 (fr)	1989-11-02	Composition détergente liquide encapsulée