EP0331370B1 - Composition détergente - Google Patents
Composition détergente Download PDFInfo
- Publication number
- EP0331370B1 EP0331370B1 EP89301851A EP89301851A EP0331370B1 EP 0331370 B1 EP0331370 B1 EP 0331370B1 EP 89301851 A EP89301851 A EP 89301851A EP 89301851 A EP89301851 A EP 89301851A EP 0331370 B1 EP0331370 B1 EP 0331370B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- liquid composition
- present
- composition according
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 51
- 239000003599 detergent Substances 0.000 title claims description 24
- 239000007788 liquid Substances 0.000 claims description 47
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 238000004851 dishwashing Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 230000009974 thixotropic effect Effects 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 4
- -1 alkalimetal hypochlorite Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 101150092843 SEC1 gene Proteins 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000007844 bleaching agent Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000036962 time dependent Effects 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
- C11D3/02—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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Definitions
- the present invention relates to detergent compositions.
- it relates to liquid machine dishwashing detergent compositions suitable for use in cleansing food soils from cooking utensils, dishes, glasses and similar ware.
- the present invention relates to a stable, pourable, aqueous system comprising at least partially undissolved builder salts and a dissolved alkali silicate, the composition being essentially free of conventional structuring agents.
- the system is characterised by its thixotropic nature.
- Detergents for use in domestic machine dishwashers are generally available in powdered or granular forms.
- solid compositions exhibit a number of disadvantages for the producer and user.
- the compositions cannot generally be spray-dried, and thus separate manufacturing facilities to those generally used for powdered detergents must be built.
- the powders often incorporate large lumps caused by caking during storage at high humidity. This can cause difficulties in dispersion. Powdered forms of the product are often very dusty, which can affect dispensing as well as causing irritation.
- liquid detergents must meet certain requirements. Firstly, the liquid must be a uniform mixture of ingredients in order to deliver the optimum combination of active components to the wash with each dose.
- active components we mean those components which actually take part in the cleaning, rather than those acting as fillers. In many formulations described in the art, this requires that the liquid be shaken before each use in order to re-mix the different components.
- a preferred product should be stable against physical separation and segregation of the active components during storage.
- Particulate solids for example detergency builders, should remain suspended in liquid detergents.
- some kind of structuring system is necessary. In aqueous detergent liquids this may be achieved either by "external structuring", ie adding an additional component such as a polymer or clay, or using the interaction of the water in the liquid and the detergent actives themselves, to form an "internal structure" to support the solids (eg secondary alkane sulphonates and phosphonates).
- external structuring ie adding an additional component such as a polymer or clay, or using the interaction of the water in the liquid and the detergent actives themselves, to form an "internal structure" to support the solids (eg secondary alkane sulphonates and phosphonates).
- microscopic investigation indicates that some type of suspending network is formed.
- the phrase 'structuring agent' as used herein is taken to mean any component, e.g. clay, polymer or biocellulosic, which at suitable amounts within a liquid imparts a structure to said liquid, usually by network formation.
- the use of such agents, particularly clay, in lower amounts is not to be taken as being excluded from compositions. Such low amounts may act as builders or rinse aids.
- the critical amount of the component in question may only be determined by reference to experiments or the prior art.
- the detergent For use with machine dishwashers, the detergent must be compatible with the dishwashing equipment presently available.
- Home dishwashing machines use a detergent cup which has been designed to house powdered or granular solid detergent and deliver it to a specific wash cycle.
- the cups are usually held vertically on the dishwasher door and are not designed to contain low viscosity liquids. Consequently, liquids for use as machine dishwashing detergents must possess sufficient viscosity to be effectively retained in the cup and avoid leakage into the machine during cycles which precede the wash. Excessive leakage will lead to under-dosing in the wash cycle and may affect cleaning performance. However, they must not be so viscous that they cannot be washed out of the dispensing cup at the appropriate time.
- GB 1 527 706 discloses a slurry structured by the addition of synthetic polymers. However, it is thought that the low yield point in liquids containing, eg polyacrylate as the only structuring agent, causes poor cup retention.
- GB 2 140 450 discloses liquids structured with clay. The clay lowers the amount of active component which can be delivered in each dose. Furthermore, the presence of insoluble clay minerals can negatively affect glass spotting and filming performance.
- the use of biopolymers or cellulosics within a liquid detergent base has also been proposed to provide thickened systems, eg US 4 226 736 and US 4 260 528.
- GB 2 185 037 has disclosed the use of long-chain fatty acids to provide a thickening effect.
- the systems described in the prior art are all, in principle, structured by the use of external, network-forming structurants and, in general, these liquids possess a shear thinning character, ie they exhibit a high viscosity at low shear rate and a low viscosity at high shear rate. Furthermore, and this illustrates the thixotropic nature of the liquids, the viscosity of these liquids is time-dependent after distortion has taken place.
- the present invention makes use of different principles to obtain pourable and stable liquid systems.
- the present invention does not involve the use of a network-forming structurant. Due to the absence of such a structurant, which in the current state of the art is judged to be essential for keeping the solid particles well suspended, the present invention involves liquid systems (dispersions) which are Newtonian (eg not shear thinning) over a broad range of shear rate values: 1-100 sec1.
- compositions of the present invention the solids are present as individual particles and not as flocculates.
- the deflocculation effect can be illustrated by the following observation: the addition of 40% zeolite 4A to a 20% sodium disilicate (ratio 3.6) solution results in the formation of a viscous, shear thinning unusable paste outside the scope of the invention. Adjusting the silicate ratio with NaOH or KOH the viscosity will drop considerably and a thin, pourable, pseudo-Newtonian system is obtained by deflocculation of the particles.
- a stable, viscous, liquid composition adapted for use in an automatic dishwasher comprising:
- the preferred rheological behaviour is identified by the Thixotropic Index (TI) which has to be between 0.5 and 2.5.
- the Thixotropic Index is herein defined as the ratio of the apparent LVT Brookfield viscosity of a sample after 3 minutes at room temperature using a No 4 spindle at (a) 3 rpm and (b) 30 rpm.
- compositions according to the present invention are formulated for ware washing, in particular for use in machine dishwashers. They have improved rheology and stability in comparison to compositions of the prior art and can deliver a high and uniform dosage of active ingredients to the machine wash cycle.
- the detergent builder material may preferably be a non-phosphate builder salt.
- Such builders include water-soluble inorganic carbonate and bicarbonate.
- Water-soluble organic builders which may be used include polyacetates, carboxylates, polycarboxylates and polyhydroxy sulphonates, at least a proportion of the salt remaining undissolved.
- Particularly preferred as builders are zeolite and amorphous silica/alumina builders.
- Aluminosilicates of the zeolite type may be prepared as described in US 2 882 243 (Union Carbide) or of the amorphous type as described in EP 0 097 512 (Unilever).
- the aluminosilicate is preferably of the formula 0.8-1.5 Na 2 0; A1 2 0 3 ; 1.7 - 3.0 Si0 2 ; 2 - 6 H 2 0.
- Examples of other suitable builders are NTA, EDTA, CMOS and DPA.
- the builder constitutes from 5-60%, preferably from 20-40%.
- the second essential component of the present invention is a silicate material.
- disilicates are particularly preferred, although metasilicates may also be included.
- the alkali-metal silicates which are used serve as anti-corrosion agents, protecting metal and china surfaces against harshly alkaline environments present during a dishwashing cycle.
- the silicate-based material constitutes from 3-40%, preferably from 5-20%.
- the present invention comprises compositions which do not necessarily contain any detergent surfactants.
- the compositions may be used for the delivery of caustic agents to the wash liquor during mechanical dishwashing operations.
- one or more detergent surfactant agents may be selected from one or more of nonionic, anionic, cationic, zwitterionc and amphoteric agents.
- Such agents are commercially available and will be well known by those skilled in the art; for instance, they are fully described in the literature, such as in "Surface Active Agents and Detergents", Volumes I and II by Schwarz, Perry and Berch.
- any detergent active material comprises one or more nonionic agents, for example the condensation products of alcohols having from 8-16 carbon atoms, and alkyl phenols with alkylene oxides including ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
- the alcohols are linear, having from 12-15 carbon atoms, and are condensed with 2-10 mols of ethylene oxide.
- Most preferred are those compounds which are generally regarded as "low- foaming", especially those where the alkylene oxide chain is terminated by a moiety other than hydrogen.
- compositions according to the present invention may be prepared by admixture of the various components.
- An alkali-metal hypochlorite may be present in the formula as an agent for removing tea, coffee and other food stains from cups, dishes, flatware, etc.
- the bleach source may be present in the mixture at from 0.1-10 wt %, with the most preferred range being from 0.1-2 wt % (percentages as active chlorine).
- Electrolytes such as NaCI, Nal, Na 2 S0 4 may be included in the composition at from 0.1 to 10 wt %.
- Defoamers may be included in the composition. These defoamers may be of the general type of slightly soluble alkyl carboxylates, alkyl phosphates, hydrophobic silicas, silicone defoamers, or many others. In addition to being an effective defoamer, the species should be stable to hypochlorite.
- the defoamer may optionally be present in the composition at from 0-5 wt %, more preferably from 0.1-1 wt %, and most preferably from 0.1-0.5 wt %.
- the products according to the present invention exhibit a high degree of stability at room temperature, in comparison to other systems. Unlike known liquids, the products produced in accordance with the present invention do not require shaking in order to redisperse the ingredients. Furthermore, compositions formulated in accordance with the present invention exhibit a higher density (1.7-1.8) than comparable products of the prior art. This is particularly important when considering transportation. A more concentrated liquid benefits from lower packing and transport costs. Also, a unit dose will deliver more active ingredients per unit dose than products produced in accordance with the art.
- Liquid systems according to the present invention are not susceptible to setting after storage. Even after prolonged storage the product does not solidify and no setting has been observed. The inference is that the product can be dosed without shaking or squeezing the bottle which is required for the current liquids with an external structurant. Dealing with bottles of 1.5-2.5 kg this benefits the convenience aspect of the product.
- compositions of the present invention provide a liquid system which is very convenient for consumers whilst being also perfectly suitable for an automatic dosing application.
- the automatic dosing principle can be used for domestic as well as industrial dishwashing machines.
- compositions according to the present invention are pourable from rest without need for shear thinning. Dispenser behaviour is strongly determined by the rheological properties of the liquid. In the prior art, Newtonian liquids are not considered to be suitable. Some of the liquids according to the present invention have been tested to measure dispenser cup leakage in a number of commercially-available dispenser types. It was found that the degree of dispenser cup leakage was acceptable if the liquid had a viscosity of at least 2000 mPAS.
- dishwashing compositions formulated according to the present invention show less tendency to cause spot formation on glass than other conventionally structured (eg by polymers or clays) liquid detergent systems. This is particularly noticeable after a number of wash cycles.
- a further possible use of the system of the invention arises when considering systems incorporating zeolite as the builder.
- Zeolite slurrys of the prior art are known to be unstable.
- JP-A-54/64504 discloses generally a zeolite slurry for detergent products, having good stability and high fluidity and consisting of an aqueous solution of a zeolite builder and a soluble alkali-metal silicate having a silica to alkali molar ratio of from 2.0 to 3.5.
- the liquids of the present invention provide a stable zeolite slurry which does not separate on standing.
- the slurry can be spray dried as a basis for formulating powders for ware washing.
- Viscosity was measured with respect to shear rate for each system.
- the composition With the addition of KOH to lower the silicate ratio, the composition exhibits pseudo-Newtonian behaviour. When no KOH is added, the liquid is shear thinning.
- log viscosity was measured as a function of log shear rate for varying additions of zeolite to the system.
- composition was found not to have separated over a period of weeks and was suitable for cleaning dishes in a machine dishwasher.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Detergent Compositions (AREA)
Claims (7)
caractérisée en ce qu'elle contient une proportion efficace d'un hydroxyde de métal alcalin de sorte que dans le silicate de métal alcalin, le rapport silice:alcali est de 0,6 à 1,9 ; en ce qu'elle ne s'amincit pas par cisaillement avec un taux de cisaillement compris entre 1 et 100 s-1 et, en ce que son indice thixotropique est compris entre 2,5 et 0,5, la composition étant essentiellement exempte d'agent structurant externe formant un réseau.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8804590 | 1988-02-26 | ||
GB888804590A GB8804590D0 (en) | 1988-02-26 | 1988-02-26 | Detergent compositions |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0331370A2 EP0331370A2 (fr) | 1989-09-06 |
EP0331370A3 EP0331370A3 (en) | 1990-07-25 |
EP0331370B1 true EP0331370B1 (fr) | 1994-10-05 |
EP0331370B2 EP0331370B2 (fr) | 1999-06-09 |
Family
ID=10632461
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89301851A Expired - Lifetime EP0331370B2 (fr) | 1988-02-26 | 1989-02-24 | Procédé de fabrication d'une composition détergente |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0331370B2 (fr) |
JP (1) | JPH07799B2 (fr) |
AU (1) | AU615517B2 (fr) |
BR (1) | BR8900868A (fr) |
CA (1) | CA1312521C (fr) |
DE (1) | DE68918612T3 (fr) |
ES (1) | ES2063812T5 (fr) |
GB (1) | GB8804590D0 (fr) |
ZA (1) | ZA891459B (fr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY111592A (en) * | 1992-08-19 | 2000-09-27 | Colgate Palmolive Co | Automatic dishwashing detergent containing an organic compound having at least one hydroxyl group |
ZA935663B (en) * | 1992-08-19 | 1995-02-06 | Colgate Palmolive Co | Cleaning composition |
WO1994004647A1 (fr) * | 1992-08-19 | 1994-03-03 | Colgate-Palmolive Company | Silicates structures et leur utilisation dans des lave-vaisselle automatiques |
TR28439A (tr) * | 1993-08-18 | 1996-06-24 | Colgate Palmolive Co | Yapilandirilmis silikatlar ve otomatik bulasik makinelerinde kullanimlari. |
EP1707624A3 (fr) | 1993-10-08 | 2007-01-03 | Novozymes A/S | Variants d'amylase |
DE19526380A1 (de) * | 1995-07-19 | 1997-01-23 | Henkel Ecolab Gmbh & Co Ohg | Pastöses Geschirreinigungsmittel und seine Herstellung |
JP6443965B2 (ja) * | 2014-07-31 | 2018-12-26 | 花王株式会社 | 液体漂白剤組成物 |
JP6655388B2 (ja) * | 2015-12-28 | 2020-02-26 | ライオン株式会社 | 食器洗い機用洗浄剤及びその製造方法、並びにスクイズ容器入り洗浄剤製品 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT330930B (de) * | 1973-04-13 | 1976-07-26 | Henkel & Cie Gmbh | Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen |
JPS5464504A (en) * | 1977-11-01 | 1979-05-24 | Nippon Chem Ind Co Ltd:The | Zeolite slurry for detergents |
JPS5464531A (en) * | 1977-11-02 | 1979-05-24 | Nippon Zeon Co Ltd | Water-dilutable coating composition |
DE3271270D1 (en) * | 1981-11-16 | 1986-06-26 | Unilever Nv | Liquid detergent composition |
GB8334250D0 (en) * | 1983-12-22 | 1984-02-01 | Albright & Wilson | Liquid detergent compositions |
MX167884B (es) * | 1983-12-22 | 1993-04-20 | Albright & Wilson | Composicion detergente liquida |
-
1988
- 1988-02-26 GB GB888804590A patent/GB8804590D0/en active Pending
-
1989
- 1989-02-20 CA CA000591551A patent/CA1312521C/fr not_active Expired - Fee Related
- 1989-02-23 AU AU30299/89A patent/AU615517B2/en not_active Ceased
- 1989-02-23 JP JP1044993A patent/JPH07799B2/ja not_active Expired - Lifetime
- 1989-02-24 ZA ZA891459A patent/ZA891459B/xx unknown
- 1989-02-24 ES ES89301851T patent/ES2063812T5/es not_active Expired - Lifetime
- 1989-02-24 BR BR898900868A patent/BR8900868A/pt not_active Application Discontinuation
- 1989-02-24 DE DE68918612T patent/DE68918612T3/de not_active Expired - Fee Related
- 1989-02-24 EP EP89301851A patent/EP0331370B2/fr not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH01261500A (ja) | 1989-10-18 |
EP0331370B2 (fr) | 1999-06-09 |
ES2063812T5 (es) | 1999-08-16 |
JPH07799B2 (ja) | 1995-01-11 |
BR8900868A (pt) | 1989-10-17 |
EP0331370A2 (fr) | 1989-09-06 |
AU3029989A (en) | 1989-08-31 |
EP0331370A3 (en) | 1990-07-25 |
DE68918612T3 (de) | 1999-08-19 |
GB8804590D0 (en) | 1988-03-30 |
DE68918612T2 (de) | 1995-02-09 |
ES2063812T3 (es) | 1995-01-16 |
AU615517B2 (en) | 1991-10-03 |
ZA891459B (en) | 1990-10-31 |
DE68918612D1 (de) | 1994-11-10 |
CA1312521C (fr) | 1993-01-12 |
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