EP0264043B1 - Verfahren zur Herstellung schmelzblockförmiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger Mittel für maschinelle Reinigen von Geschirr - Google Patents
Verfahren zur Herstellung schmelzblockförmiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger Mittel für maschinelle Reinigen von Geschirr Download PDFInfo
- Publication number
- EP0264043B1 EP0264043B1 EP87114488A EP87114488A EP0264043B1 EP 0264043 B1 EP0264043 B1 EP 0264043B1 EP 87114488 A EP87114488 A EP 87114488A EP 87114488 A EP87114488 A EP 87114488A EP 0264043 B1 EP0264043 B1 EP 0264043B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- melt
- active chlorine
- water
- triphosphate
- 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
- 150000008044 alkali metal hydroxides Chemical class 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000460 chlorine Substances 0.000 title claims description 19
- 229910052801 chlorine Inorganic materials 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003795 chemical substances by application Substances 0.000 title description 7
- 229910001854 alkali hydroxide Inorganic materials 0.000 title description 6
- 238000004140 cleaning Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000155 melt Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000001226 triphosphate Substances 0.000 claims abstract description 14
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 235000011178 triphosphate Nutrition 0.000 claims abstract description 6
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011362 coarse particle Substances 0.000 claims abstract 2
- 239000010419 fine particle Substances 0.000 claims abstract 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 9
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 7
- 238000004851 dishwashing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- 239000011734 sodium Substances 0.000 abstract description 6
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 2
- 150000007973 cyanuric acids Chemical class 0.000 abstract 1
- SJUGPXBWZCQTKM-UHFFFAOYSA-N n-chloro-4-methylbenzenesulfonamide;sodium Chemical compound [Na].CC1=CC=C(S(=O)(=O)NCl)C=C1 SJUGPXBWZCQTKM-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 14
- 235000021317 phosphate Nutrition 0.000 description 14
- 239000012459 cleaning agent Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 235000019795 sodium metasilicate Nutrition 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- -1 dichloroisocyanurate dihydrate Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000013042 solid detergent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 240000008104 Stachytarpheta jamaicensis Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0052—Cast detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3958—Bleaching agents combined with phosphates
Definitions
- Solid detergents for automatic dishwashing are mainly offered in powder or granular form (agglomerates).
- the individual particles of these agents have a preferred diameter between 0.01 and 3 mm.
- a serious disadvantage of this type of solid cleaning agents, especially those used in the field of large-scale commercial use with a content of 10 to 60% by weight of alkali metal hydroxides, is that, due to the hygroscopicity of individual raw materials, small amounts of moisture have a strong tendency to Baked or clumped.
- a disadvantage is the use of cleaning agents that tend to clump or cake when exposed to moisture, especially in automatic, stocking dosing devices that are used in large numbers in the area of large-scale commercial use of single-tank and multi-tank dishwashers.
- cleaning agents that tend to clump or cake when exposed to moisture
- the only remedy is to prevent the entry of moisture into the storage container, but this cannot be guaranteed in a damp kitchen atmosphere or after cleaning the device with water without drying the parts of the storage container and the dosing device.
- the clumping or caking of alkaline cleaning agents can be avoided, among other things, by producing them in block form from the outset and packing, distributing and using them in a moisture-proof manner.
- melt-block detergents for automatic dishwashing have already been described, which are mixed together by mixing all alkaline-reacting, preferably hydrate-containing active substances, such as. B. sodium silicates, pentasodium triphosphate, sodium hydroxide and optionally water, if the preferred water of hydration of the compounds mentioned is not sufficient, and then mild heating of the mixture with stirring to 90 to 100 ° C. until a uniformly molten mass was obtained and cast in molds and solidified to form a dense crystal aggregate.
- active substances such as. B. sodium silicates, pentasodium triphosphate, sodium hydroxide and optionally water
- EP-PS 3 769 describes detergent containers, in particular for machine dishwashing, which contain solid detergent blocks, made from water and two solid constituents, at least one of which is an alkaline hydratable compound and are only open at one point then the detergent is rinsed out by the water flow in the washing machine.
- these cleaning agents are to contain active chlorine compounds in addition to alkali hydroxide, which are necessary for the removal of bleachable soiling, such as, for. B. tea, coffee, fruit juices, etc. are considered, these must preferably be introduced as preformed kernels during the solidification of the cleaning agent in the still soft mass.
- the core should still be coated either with paraffin or with a wax-like mono- and dialkyl ester of polyphosphoric acid.
- Example 13 shows that a direct addition of the active chlorine-releasing compound to the melt mass leads to a high loss of active chlorine within 24 hours.
- the investigated chlorine carriers were Ca (OCl) 2, LiOCl and Na dichloroisocyanurate dihydrate. Depending on the chlorine carrier, residual chlorine activities between only 3.5 and 17.4% of the initial value were determined.
- the invention now relates to a process for the preparation of alkali metal-containing melt-block-shaped, homogeneous and storage-stable agents for the mechanical cleaning of dishes containing alkali silicates and water, preferably as water of crystallization, pentaalkali metal phosphate and optionally a further content of active chlorine-releasing compounds and / or organic complexing agents characterized in that first a melt consisting of alkali silicates, alkali hydroxides and optionally water is generated and this is tempered by cooling or heating to 50-75 ° C, preferably 55-70 ° C, then optionally under careful control at a temperature of incorporates an active chlorine-releasing compound and / or organic complexing agent below 70 ° C., the melt obtained simultaneously with the pentaalkali metal phosphate fraction and, if appropriate, other customary components for such agents in a continuous mixer g ibt, where the additional solid, powder or granular raw materials are distributed in the melt, and the still liquid overall mixture immediately afterwards poured into arbitr
- a continuous mixer those can be used which are also suitable for the production of suspensions or pastes. Preferred are those which bring about a homogeneous distribution of the pentasodium triphosphate in the melt with short residence times of less than one minute and the narrowest possible residence time spectrum, for example an injection mixer from FMC.
- the feed and discharge lines of the mixer are heated so that their internal temperatures are 50 to 75 ° C and correspond to those of the melt. At higher temperatures, partial degradation of the active chlorine carrier is to be feared others also favor the phosphate breakdown in the melt after pouring into the molds. Lower temperatures can lead to at least partial crystallization of the melt in the batching tank, the metering units, the pipelines or the mixer and thereby cause technical malfunctions.
- alkali hydroxide potassium and, for reasons of price, preferably sodium hydroxide are suitable, which are preferably in solid form, ie. H. as flakes, flakes or prills, practically anhydrous or as a monohydrate.
- aqueous alkali hydroxide solutions can also be used. Only the water content for the overall composition has to be taken into account.
- the amounts used are advantageously 2 to 70, preferably 5 to 50% by weight, anhydrous, based on the total composition.
- Alkali silicates in particular are alkali metal silicates, namely water-free, but advantageously in the form of sodium metasilicate. 9 H2O, sodium metasilicate. 6 H2O and sodium metasilicate. 5 H2O used.
- the amounts used in the particular form are expediently 0 to 60, preferably 0 to 50,% by weight, based on the total composition. But you can also partially or completely replace the alkali metal silicates with water glass solutions, the ratio of Na2O: SiO2 being 1: 1 to 1: 4, preferably 1: 2 to 1: 3.5. Because of the higher silicate content of the water glass, its solutions are expediently used in amounts of 0 to 30, preferably 0 to 15,% by weight, based on the total agent.
- Suitable organic complexing agents which can be solubility-improving constituents of the melt-block-shaped cleaning agents, are polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, in particular polymeric carboxylic acids and phosphonic acids. these compounds being used in the form of their water-soluble salts.
- the amount of organic complexing agents is advantageously 0 to 10, preferably 0 to 5% by weight, based on the total agent.
- the blocks are then no longer composed homogeneously, so that a dosage according to the recipe is not guaranteed during use (gradual rinsing of the blocks).
- the weight ratio of the two types of phosphate to one another can vary within wide limits. In the case of highly alkaline formulations, ratios of coarse-grained to fine-grained phosphate of approximately 10: 1 to 2: 1, preferably 6: 1 to 3: 1, have proven successful. In the case of low-alkaline formulations, degrees of phosphate maintenance of more than 90% are already achieved even with fine-grained phosphate. A total of 2 to 50, preferably 5 to 45,% by weight of pentaalkali phosphate is expediently used.
- the total water content of the melt-block-shaped cleaning agents from dense crystal aggregates is essentially 10 to 40, preferably 15 to 30% by weight. It is preferably introduced by the crystal water content of the alkaline reacting substances, but possibly also via water glass solutions. The calculations of the water content must therefore be based on these compounds.
- the solidification process of the melts obtained by the process according to the invention takes from a few minutes to about one hour, depending on the size of the mold and the composition of the mass. Depending on their composition, the finished melting blocks are very hard, hard or less hard, but in any case through and by consistently composed and quickly soluble in use.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87114488T ATE73487T1 (de) | 1986-10-13 | 1987-10-05 | Verfahren zur herstellung schmelzblockfoermiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger mittel fuer maschinelle reinigen von geschirr. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3634812 | 1986-10-13 | ||
DE19863634812 DE3634812A1 (de) | 1986-10-13 | 1986-10-13 | Verfahren zur herstellung schmelzblockfoermiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger mittel fuer das maschinelle reinigen von geschirr |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0264043A2 EP0264043A2 (de) | 1988-04-20 |
EP0264043A3 EP0264043A3 (en) | 1989-02-01 |
EP0264043B1 true EP0264043B1 (de) | 1992-03-11 |
Family
ID=6311618
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87114488A Expired - Lifetime EP0264043B1 (de) | 1986-10-13 | 1987-10-05 | Verfahren zur Herstellung schmelzblockförmiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger Mittel für maschinelle Reinigen von Geschirr |
Country Status (6)
Country | Link |
---|---|
US (1) | US5064554A (es) |
EP (1) | EP0264043B1 (es) |
AT (1) | ATE73487T1 (es) |
DE (2) | DE3634812A1 (es) |
ES (1) | ES2029467T3 (es) |
GR (1) | GR3004644T3 (es) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU4051289A (en) * | 1989-03-31 | 1990-11-05 | Ecolab Inc. | Cast detersive systems |
NZ239112A (en) | 1991-01-29 | 1994-12-22 | Ecolab Inc | Solid alkaline compositions containing the reaction product in water of alkali metal hydroxide and alkali metal silicate; process of manufacture |
US5209864A (en) * | 1991-07-03 | 1993-05-11 | Winbro Group, Ltd. | Cake-like detergent and method of manufacture |
AU1516795A (en) * | 1993-12-30 | 1995-07-17 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
EP0737244B1 (en) * | 1993-12-30 | 1998-07-15 | Ecolab Inc. | Method of making highly alkaline solid cleaning compositions |
US6489278B1 (en) | 1993-12-30 | 2002-12-03 | Ecolab Inc. | Combination of a nonionic silicone surfactant and a nonionic surfactant in a solid block detergent |
US6673765B1 (en) | 1995-05-15 | 2004-01-06 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
US6387870B1 (en) | 1999-03-29 | 2002-05-14 | Ecolab Inc. | Solid pot and pan detergent |
US6369021B1 (en) | 1999-05-07 | 2002-04-09 | Ecolab Inc. | Detergent composition and method for removing soil |
US6471974B1 (en) | 1999-06-29 | 2002-10-29 | S.C. Johnson & Son, Inc. | N-chlorosulfamate compositions having enhanced antimicrobial efficacy |
JP3832399B2 (ja) * | 2001-08-28 | 2006-10-11 | 栗田工業株式会社 | 殺菌殺藻剤組成物及び水系の殺菌殺藻方法 |
DE102005004761B4 (de) * | 2005-02-01 | 2009-04-02 | Witty Chemie Gmbh & Co. Kg | Reinigungsmittel zur Grundreinigung von Spülgut in einer Geschirrspülmaschine und Verfahren zur Steuerung der Reinigungszyklen in einer Geschirrspülmaschine |
US20060234900A1 (en) * | 2005-04-13 | 2006-10-19 | Ecolab Inc. | Composition and process for preparing a phosphonate and phosphate-free automatic dishwashing powder |
JP6462028B2 (ja) * | 2016-03-31 | 2019-01-30 | 株式会社Adeka | 溶融固形型洗浄剤組成物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2412819A (en) * | 1945-07-21 | 1946-12-17 | Mathieson Alkali Works Inc | Detergent briquette |
US4569780A (en) * | 1978-02-07 | 1986-02-11 | Economics Laboratory, Inc. | Cast detergent-containing article and method of making and using |
US4569781A (en) * | 1978-02-07 | 1986-02-11 | Economics Laboratory, Inc. | Cast detergent-containing article and method of using |
IT1110274B (it) * | 1978-02-07 | 1985-12-23 | Economics Lab | Articolo contenente detersivo colato e metodo di sua preparazione e suo impiego |
GB2061996B (en) * | 1979-09-21 | 1983-06-22 | Jeyes Group Ltd | Lavatory cleansing blocks |
DE3519355A1 (de) * | 1985-05-30 | 1986-12-04 | Henkel KGaA, 4000 Düsseldorf | Schmelzblockfoermige, alkalihydroxid- und aktivchlorhaltige mittel fuer das maschinelle reinigen von geschirr und verfahren zu ihrer herstellung |
DE3519354A1 (de) * | 1985-05-30 | 1986-12-04 | Henkel KGaA, 4000 Düsseldorf | Schmelzblockfoermiges alkalihydroxidfreies mittel fuer das maschinelle reinigen von geschirr und verfahren zu seiner herstellung |
DE3519353A1 (de) * | 1985-05-30 | 1986-12-04 | Henkel KGaA, 4000 Düsseldorf | Schmelzblockfoermige, alkalihydroxidhaltige mittel fuer das maschinelle reinigen von geschirr und verfahren zu ihrer herstellung |
-
1986
- 1986-10-13 DE DE19863634812 patent/DE3634812A1/de not_active Withdrawn
-
1987
- 1987-10-05 EP EP87114488A patent/EP0264043B1/de not_active Expired - Lifetime
- 1987-10-05 AT AT87114488T patent/ATE73487T1/de active
- 1987-10-05 ES ES198787114488T patent/ES2029467T3/es not_active Expired - Lifetime
- 1987-10-05 DE DE8787114488T patent/DE3777318D1/de not_active Expired - Fee Related
- 1987-10-09 US US07/107,235 patent/US5064554A/en not_active Expired - Fee Related
-
1992
- 1992-05-18 GR GR920400977T patent/GR3004644T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
DE3634812A1 (de) | 1988-04-14 |
EP0264043A3 (en) | 1989-02-01 |
EP0264043A2 (de) | 1988-04-20 |
US5064554A (en) | 1991-11-12 |
ES2029467T3 (es) | 1992-08-16 |
ATE73487T1 (de) | 1992-03-15 |
GR3004644T3 (es) | 1993-04-28 |
DE3777318D1 (de) | 1992-04-16 |
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