EP0110106B1 - Stable, aqueous detergents and process for their preparation - Google Patents
Stable, aqueous detergents and process for their preparation Download PDFInfo
- Publication number
- EP0110106B1 EP0110106B1 EP83110508A EP83110508A EP0110106B1 EP 0110106 B1 EP0110106 B1 EP 0110106B1 EP 83110508 A EP83110508 A EP 83110508A EP 83110508 A EP83110508 A EP 83110508A EP 0110106 B1 EP0110106 B1 EP 0110106B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chlorine
- optionally
- weight
- stable
- abrasive
- 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
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 5
- 230000008569 process Effects 0.000 title claims abstract description 4
- 239000003599 detergent Substances 0.000 title description 2
- 239000000460 chlorine Substances 0.000 claims abstract description 47
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 47
- 238000011065 in-situ storage Methods 0.000 claims abstract description 22
- 125000000129 anionic group Chemical group 0.000 claims abstract description 9
- 239000000975 dye Substances 0.000 claims abstract description 8
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002304 perfume Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 claims 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 239000000404 calcium aluminium silicate Substances 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 239000003205 fragrance Substances 0.000 abstract description 14
- 239000012459 cleaning agent Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 9
- -1 calcium aluminum silicates Chemical class 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000003082 abrasive agent Substances 0.000 description 27
- 239000007788 liquid Substances 0.000 description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 19
- 239000000725 suspension Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 239000007844 bleaching agent Substances 0.000 description 10
- 235000013339 cereals Nutrition 0.000 description 10
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000004061 bleaching Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000004579 marble Substances 0.000 description 7
- 238000009991 scouring Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 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 6
- 239000003086 colorant Substances 0.000 description 5
- 235000011837 pasties Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- IQDXNHZDRQHKEF-UHFFFAOYSA-N dialuminum;dicalcium;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O IQDXNHZDRQHKEF-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 230000009974 thixotropic effect Effects 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 240000003834 Triticum spelta Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000019362 perlite Nutrition 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- YVKMMZAFUFUAAX-UHFFFAOYSA-N aluminum;tetrahydrate Chemical compound O.O.O.O.[Al] YVKMMZAFUFUAAX-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000013799 ultramarine blue 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D3/1286—Stabilised aqueous aluminosilicate suspensions
-
- 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
- C11D3/3956—Liquid compositions
Definitions
- the present invention relates to aqueous, storage- and action-stable liquid or pasty cleaning agents containing in particular chlorine-stable surfactants, an abrasive component and / or active chlorine-releasing compound, colorants and fragrances and calcium aluminum silicate precipitated in situ.
- Bleaching detergents or abrasives should have this effect in the shortest possible time, namely during their use and at room temperature.
- Compounds which release active chlorine are known as technically available bleaching agents for such liquid compositions which meet these conditions and whose loss of action can be tolerated in aqueous solution.
- EP-A-0003625 also teaches that swellable clays are used to stabilize the suspension of hypochlorite-containing liquid abrasives.
- they have the disadvantage that they have such a strong thickening effect that they can only be used in small quantities and only for the stabilization of the suspension of specifically light abrasives, namely from there preferred and exclusively used expanded perlites, but not for the stabilization of those also mentioned there and usually in real ones
- Abrasives that are used, specifically heavy abrasives such as quartz or marble powder are suitable in amounts required for sufficient abrasion performance. These sediment even through thixotropic pastes and form an irreversible sediment.
- aqueous, storage- and action-stable liquid or pasty, cleaning or abrasives containing anionic and / or nonionic, in particular chlorine-stable surfactants and an abrasive component and / or an active chlorine-releasing compound are obtained if they are amorphous Calcium aluminum silicates are added, which are precipitated in situ, if appropriate in the presence of the abrasives which are preferably present.
- the suspension-stabilizing effect of Ca-AI silicate precipitated in situ has hitherto not been known and could not have been foreseen by the person skilled in the art.
- the Ca-AI silicate is obtained in X-ray amorphous form, has no swellability in water and, of course, no complexing effect against hardness-forming ions in the tap water. Because of these properties, there is no analogy to other silicates known as components of cleaning agents.
- the Ca-Al silicate is produced in situ, preferably in the presence of abrasives. If it is manufactured separately and subsequently added to the liquid cleaning agent or abrasive, the suspension stabilization is significantly lower. Scanning electron micrographs show that, for example, CaC0 3 particles used as abrasives in abrasives according to the invention are coated with a uniform layer of smaller solid particles in the case of Ca-Al silicate precipitated in situ.
- the CaC0 3 particles are otherwise the same composition with a subsequently added equal amount of precipitated Ca-Al silicate, or Zu given a corresponding amount of commercially available hectorite clay (Na-Mg silicate), unchanged as a mixture with the finer solid particles.
- the agents according to the invention can also contain colorants and fragrances, which may have to be chlorine-stable.
- the invention relates to a process for the preparation of aqueous storage-stable and action-stable liquid or pasty cleaning or abrasive agents with a content of optionally chlorine-stable anionic and / or nonionic surfactants, an abrasive component and / or an active chlorine-releasing compound, and optionally colorants and fragrances, which is characterized in that the abrasive component is optionally stirred into an aqueous solution of the surfactants and optionally the dyes at room temperature and, with further stirring, a calcium chloride solution, then an aluminum hydroxide solution, then a water glass solution and optionally the chlorine solution and the fragrance are added.
- a certain pH value of the end product is to be set, which, however, should not be below 11.5 in the case of chlorine-containing cleaning agents for the known reasons of chlorine stability, this can be between the addition of the aluminate solution and the water glass solution with a chlorine-stable acid such as e.g. Hydrochloric acid, phosphoric acid or phosphonobutane tricarboxylic acid can be set.
- a chlorine-stable acid such as e.g. Hydrochloric acid, phosphoric acid or phosphonobutane tricarboxylic acid
- a cleaning agent without abrasives can also be produced with the Ca-AI silicate according to the invention.
- a thickened, thixotropic, preferably chlorine-containing cleaning agent is then obtained with only an extremely weak abrasive effect.
- a product has the advantage of adhering better to vertical surfaces, which has a positive effect on the quality of the bleaching effect.
- Such agents are known for example from DE-A-2810187.
- the cleaning agents according to the invention are opaque, white suspensions which, even after prolonged storage, either do not separate at all or only so weakly that they can be homogenized again by gently shaking them before use.
- the claimed agents are applied by pushing them out of soft plastic bottles or tubes.
- the liquid abrasive obtained was thixotropic, had a relatively mild abrasive action and a very good bleaching action. After 1 ⁇ 4 year storage at room temperature, the suspension was unchanged and the chlorine loss was only about 22%.
- Example 2 The preparation was carried out analogously to Example 1. It was a thixotropic abrasive paste with a weak abrasive effect. After 3 months of storage, the suspension remained homogeneous. The active chlorine content was practically retained.
- the liquid abrasive had properties similar to those of Example 1; the active chlorine loss after 3 months' storage at room temperature was only about 20%.
- alkanesulfonate Na salt 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% chlorine bleach, 12-16% active chlorine, 45.0% marble powder, average particle diameter 15 ⁇ m , 5.6% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.
- alkanesulfonate Na salt 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% Chlorine bleach, 12-16% active chlorine, 13.0% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.
- This abrasive-free, active chlorine-containing thickened cleaning agent was also produced analogously to Example 1.
- This paste which also adhered well to vertical surfaces, was still homogeneous even after 6 months of storage at room temperature and the chlorine loss was less than 50%.
- the preparation was carried out analogously to Example 1, the copolymer was added after the marble powder. Before adding the water glass, a pH of 12.5 was set with dilute hydrochloric acid, which did not change after the liquid abrasive was finished.
- the pourable, bleaching abrasive showed similarly good storage results to both the suspension stability and the chlorine stability as the aforementioned examples.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft wässrige, lager- und wirkungsstabile flüssige oder pastöse Reinigungsmittel mit einem Gehalt an insbesondere chlorstabilen Tensiden, einer Abrasivstoffkomponente und/oder aktivchlorabgebenden Verbindung, Farb- und Duftstoffen sowie in situ gefälltem Calcium-Aluminium-Silikat.The present invention relates to aqueous, storage- and action-stable liquid or pasty cleaning agents containing in particular chlorine-stable surfactants, an abrasive component and / or active chlorine-releasing compound, colorants and fragrances and calcium aluminum silicate precipitated in situ.
Für die Reinigung stark verschmutzter, mechanisch widerstandsfähiger Oberflächen im Haushalt und Gewerbe werden grosse Mengen an Scheuermitteln verbraucht. Dabei werden auf dem Markt, je etwa zur Hälfte, pulverförmige Scheuermittel mit und ohne bleichende Wirkung angeboten. Nichtbleichende Scheuerpulver werden zurzeit in wachsendem Masse durch flüssige Scheuermittel substituiert. Bisher ist aber noch kein echtes, flüssiges und bleichend wirkendes Scheuermittel auf dem Markt anzutreffen. Der Grund dürfte in der Schwierigkeit zu sehen sein, derartige Produkte in lagerstabiler Form zu konfektionieren, und zwar sowohl im Hinblick auf die Suspension als auch auf die Bleichwirkstoffstabilität.Large amounts of abrasives are used to clean heavily soiled, mechanically resistant surfaces in the home and business. Powdered abrasives with and without bleaching effects are offered on the market, about half each. Non-bleaching scouring powders are currently being increasingly replaced by liquid scouring agents. So far, however, there is no real, liquid and bleaching abrasive on the market. The reason should be seen in the difficulty of assembling such products in a storage-stable form, both with regard to the suspension and the bleaching agent stability.
Bleichend wirkende Reinigungs- bzw. Scheuermittel sollen diese Wirkung in kürzester Zeit, nämlich während ihrer Anwendung und bei Raumtemperatur, entfalten. Als technisch verfügbare Bleichwirkstoffe für solche flüssigen Mittel, die diese Bedingungen erfüllen und deren Wirkungsverlust in wässriger Lösung tolerierbar ist, sind aktivchlorabspaltende Verbindungen bekannt. Für die Herstellung eines flüssigen Reinigungs- bzw. Scheuermittels, insbesondere auf Basis dieser Verbindungen stellte sich nun die Aufgabe, ein vor allem gegen wässrige aktivchlorhaltige Lösungen beständiges Medium zu finden, das einerseits in der Lage ist, gegebenenfalls auch Abrasivstoffteilchen lagerstabil zu suspendieren und das andererseits grenzflächenaktive Eigenschaften aufweisen soll, damit das flüssige Reinigungs- bzw. Scheuermittel neben der reinen Scheuer- und/ oder Bleichleistung auch die vom Verbraucher erwartete Reinigungswirkung gegenüber fetthaltigen Verschmutzungen entfaltet.Bleaching detergents or abrasives should have this effect in the shortest possible time, namely during their use and at room temperature. Compounds which release active chlorine are known as technically available bleaching agents for such liquid compositions which meet these conditions and whose loss of action can be tolerated in aqueous solution. For the production of a liquid cleaning agent or scouring agent, in particular based on these compounds, the task now was to find a medium which is particularly resistant to aqueous solutions containing active chlorine and which, on the one hand, is capable of suspending abrasive particles, if necessary, on storage, and on the other hand should have surface-active properties, so that the liquid cleaning or scouring agent, in addition to the pure scouring and / or bleaching performance, also has the cleaning effect expected by the consumer against greasy soiling.
In der US-A-4248728 werden schon pastenförmige Scheuermittel mit einem Gehalt an kristallinem Na-AI-Silikat, sowie wahlweise aktivchlorhaltigen Verbindungen und/oder mineralischen Abrasivstoffen beschrieben. Die nach der Lehre dieses US-Patentes unter Zusatz von quellfähigem Mg-AI-Silikat hergestellten abrasivstoffhaltigen Beispiele ergeben zwar pastenförmige Scheuermittel, jedoch setzen sich die Abrasivstoffe trotz gegenteiliger, allerdings unspezifischer Aussagen, nach Lagerung irreversibel zu einem festen Bodensatz ab. Damit ist das Produkt nicht mehr einsatzfähig.In US-A-4248728 pasty abrasives containing crystalline Na-Al-silicate and optionally active chlorine-containing compounds and / or mineral abrasives are already described. The abrasive-containing examples produced according to the teaching of this US patent with the addition of swellable Mg-Al-silicate result in paste-like abrasives, but despite contrary but unspecific statements, the abrasives settle irreversibly to a solid sediment after storage. This means that the product is no longer operational.
Auch in der EP-A-0003625 wird gelehrt, zur Suspensionsstabilisierung hypochlorithaltiger flüssiger Scheuermittel quellfähige Tone zu verwenden. Sie haben aber den Nachteil, dass sie so stark verdickend wirken, dass sie nur in geringen Mengen einsetzbar sind und nurzurSuspensionsstabilisierung spezifisch leichter Abrasiva, nämlich von dort bevorzugt und ausschliesslich verwendeten expandierten Perliten, nicht jedoch zur Stabilisierung von zwar dort auch genannten und üblicherweise in echten Scheuermitteln eingesetzten, spezifisch schweren Abrasiva wie Quarz- oder Marmormehl in für eine ausreichende Scheuerleistung notwendigen Einsatzmengen geeignet sind. Diese sedimentieren selbst durch thixotrope Pasten hindurch und bilden einen irreversiblen Bodensatz. Ein weiterer Nachteil ist darin zu sehen, dass diese quellfähigen Tone aufgrund ihrer natürlichen Herkunft meist geringe Mengen an Verunreinigungen enthalten, welche über katalytische Reaktionen den Zerfall aktivchlorhaltiger Verbindungen in wässriger Lösung beschleunigen und damit ihre langfristige Wirkungsstabilität in den flüssigen Reinigungs- bzw. Scheuermitteln verschlechtern.EP-A-0003625 also teaches that swellable clays are used to stabilize the suspension of hypochlorite-containing liquid abrasives. However, they have the disadvantage that they have such a strong thickening effect that they can only be used in small quantities and only for the stabilization of the suspension of specifically light abrasives, namely from there preferred and exclusively used expanded perlites, but not for the stabilization of those also mentioned there and usually in real ones Abrasives that are used, specifically heavy abrasives such as quartz or marble powder, are suitable in amounts required for sufficient abrasion performance. These sediment even through thixotropic pastes and form an irreversible sediment. Another disadvantage is the fact that these swellable clays usually contain small amounts of impurities due to their natural origin, which accelerate the decomposition of active chlorine-containing compounds in aqueous solution via catalytic reactions and thus worsen their long-term effectiveness in the liquid cleaning or abrasive agents.
Aus der EP-A-0009942 sind ebenfalls giessbare flüssige aktivchlorhaltige Scheuermittel bekannt, die eine Kombination aus anionischen und nichtionischen oder ampholytischen Tensiden und einem Elektrolyten enthalten. Die Chlorstabilität dieser Scheuermittelsuspensionen ist jedoch für Verkaufsprodukte nicht ausreichend.Also known from EP-A-0009942 are pourable liquid active chlorine-containing abrasives which contain a combination of anionic and nonionic or ampholytic surfactants and an electrolyte. However, the chlorine stability of these abrasive suspensions is not sufficient for sales products.
Es wurde nun gefunden, dass man wässrige, lager- und wirkungsstabile flüssige oder pastöse, Reinigungs- bzw. Scheuermittel mit einem Gehalt an anionischen und/oder nichtionischen, insbesondere chlorstabilen Tensiden und einer Abrasivstoffkomponente und/oder einer aktivchlorabgebenden Verbindungen erhält, wenn man ihnen amorphe Calcium-Aluminium-Silikate zusetzt, die, gegebenenfalls in Gegenwart der bevorzugt vorhandenen Abrasivstoffe, in situ gefällt werden.It has now been found that aqueous, storage- and action-stable liquid or pasty, cleaning or abrasives containing anionic and / or nonionic, in particular chlorine-stable surfactants and an abrasive component and / or an active chlorine-releasing compound are obtained if they are amorphous Calcium aluminum silicates are added, which are precipitated in situ, if appropriate in the presence of the abrasives which are preferably present.
Die suspensionsstabilisierende Wirkung von in situ gefälltem Ca-AI-Silikat ist bisher nicht bekannt und für den Fachmann nicht voraussehbar gewesen. Das Ca-AI-Silikat fällt in röntgenamorpher Form an, besitzt keine Quellfähigkeit in Wasser und selbstverständlich keine Komplexierwirkung gegenüber Härtebildner-lonen des Leitungswassers. Aufgrund dieser Eigenschaften ist keine Analogie zu anderen Silikaten, die als Bestandteile von Reinigungsmitteln bekannt sind, gegeben.The suspension-stabilizing effect of Ca-AI silicate precipitated in situ has hitherto not been known and could not have been foreseen by the person skilled in the art. The Ca-AI silicate is obtained in X-ray amorphous form, has no swellability in water and, of course, no complexing effect against hardness-forming ions in the tap water. Because of these properties, there is no analogy to other silicates known as components of cleaning agents.
Neben den chemischen Unterschieden zwischen den aus Literatur und Praxis bekannten und bewährten Silikaten und dem beanspruchten Ca-AI-Silikat ist es ein wesentliches Merkmal der vorliegenden Erfindung, dass das Ca-AI-Silikat, vorzugsweise in Gegenwart von Abrasivstoffen, in situ erzeugt wird. Wird es separat hergestellt und dem flüssigen Reinigungs- bzw. Scheuermittel nachträglich zugefügt, ist die Suspensionsstabilisierung deutlich geringer. Rasterelektronenmikroskopische Aufnahmen lassen erkennen, dass beispielsweise in erfindungsgemässen Scheuermitteln als Abrasivstoffe eingesetzte CaC03-Teilchen bei in situ gefälltem Ca-AI-Silikat mit einer gleichmässigen Schicht kleinerer Feststoffteilchen überzogen sind. Dagegen liegen die CaC03-Teilchen bei sonst gleicher Zusammensetzung mit einer nachträglich zugesetzten gleichen Menge an vorgefälltem Ca-Al-Silikat, beziehungsweise bei Zugabe einer entsprechenden Menge an handelsüblichem Hectorit-Ton (Na-Mg-Silikat), unverändert als Gemenge mit den feineren Feststoffteilchen vor.In addition to the chemical differences between the silicates known and proven from literature and practice and the claimed Ca-Al silicate, it is an essential feature of the present invention that the Ca-Al silicate is produced in situ, preferably in the presence of abrasives. If it is manufactured separately and subsequently added to the liquid cleaning agent or abrasive, the suspension stabilization is significantly lower. Scanning electron micrographs show that, for example, CaC0 3 particles used as abrasives in abrasives according to the invention are coated with a uniform layer of smaller solid particles in the case of Ca-Al silicate precipitated in situ. In contrast, the CaC0 3 particles are otherwise the same composition with a subsequently added equal amount of precipitated Ca-Al silicate, or Zu given a corresponding amount of commercially available hectorite clay (Na-Mg silicate), unchanged as a mixture with the finer solid particles.
Die erfindungsgemässen Mittel können in einer besonderen Ausführungsform noch Farb- und Duftstoffe enthalten, die gegebenenfalls chlorstabil sein müssen.In a particular embodiment, the agents according to the invention can also contain colorants and fragrances, which may have to be chlorine-stable.
Die vorliegende Erfindung betrifft somit wässrige lager- und wirkstoffstabile flüssige oder pastöse Reinigungs- bzw. Scheuermittel mit einem Gehalt an
- a) 1-10, vorzugsweise 2-6 Gew.-%, gegebenenfalls chlorstabilen anionischen und/oder nichtionischen Tensiden,
- b) 0-10, vorzugsweise 0,1-2 Gew.-% Aktivchlor,
- c) 0-60, vorzugsweise 10-50 Gew.-% einer Abrasivkomponente mit einer Korngrösse von 1-200 µm,
- d) 5-20, vorzugsweise 5-15 Gew.-%, gegebenenfalls in Gegenwart der Abrasivkomponente, in situ gefälltem Calcium-Aluminium-Silikat,
- e) Rest auf 100 Gew.-% vollentsalztes Wasser sowie gegebenenfalls Farb- und Duftstoffen, wobei wenigstens einer der Bestandteile b) oder c) vorhanden sein muss.
- a) 1-10, preferably 2-6% by weight, optionally chlorine-stable anionic and / or nonionic surfactants,
- b) 0-10, preferably 0.1-2% by weight of active chlorine,
- c) 0-60, preferably 10-50% by weight of an abrasive component with a grain size of 1-200 µm,
- d) 5-20, preferably 5-15% by weight, optionally in the presence of the abrasive component, calcium aluminum silicate precipitated in situ,
- e) the remainder to 100% by weight of demineralized water and, if appropriate, colorants and fragrances, at least one of the constituents b) or c) being present.
Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung wässriger lager- und wirkungsstabiler flüssiger oder pastöser Reinigungs- bzw. Scheuermittel mit einem Gehalt an gegebenenfalls chlorstabilen anionischen und/oder nichtionischen Tensiden, einer Abrasivstoffkomponente und/oder einer aktivchlorabgebenden Verbindung, sowie gegebenenfalls Farb- und Duftstoffen, das dadurch gekennzeichnet ist, dass man bei Raumtemperatur gegebenenfalls die Abrasivstoffkomponente in eine wässrige Lösung der Tenside sowie gegebenenfalls der Farbstoffe einrührt und unter weiterem Rühren eine Calciumchloridlösung, anschliessend eine Aluminiumhydroxidlösung, danach eine Wasserglaslösung sowie gegebenenfalls die Chlorlauge und den Duftstoff zufügt.Furthermore, the invention relates to a process for the preparation of aqueous storage-stable and action-stable liquid or pasty cleaning or abrasive agents with a content of optionally chlorine-stable anionic and / or nonionic surfactants, an abrasive component and / or an active chlorine-releasing compound, and optionally colorants and fragrances, which is characterized in that the abrasive component is optionally stirred into an aqueous solution of the surfactants and optionally the dyes at room temperature and, with further stirring, a calcium chloride solution, then an aluminum hydroxide solution, then a water glass solution and optionally the chlorine solution and the fragrance are added.
Falls ein bestimmter pH-Wert des Endproduktes eingestellt werden soll, der jedoch im Fall chlorhaltiger Reinigungsmittel aus den bekannten Gründen der Chlorstabilität nicht unter 11,5 liegen sollte, kann dieser zwischen der Zugabe der Aluminatlösung und der Wasserglaslösung mit einer chlorstabilen Säure wie z.B. Salzsäure, Phosphorsäure oder Phosphonobutantricarbonsäure eingestellt werden.If a certain pH value of the end product is to be set, which, however, should not be below 11.5 in the case of chlorine-containing cleaning agents for the known reasons of chlorine stability, this can be between the addition of the aluminate solution and the water glass solution with a chlorine-stable acid such as e.g. Hydrochloric acid, phosphoric acid or phosphonobutane tricarboxylic acid can be set.
Obwohl der eigentliche Nutzen der vorliegenden Erfindung in der Suspensionsstabilisierung von Abrasivstoffen mit Korngrössen bis 200 µm in flüssigen Scheuermitteln liegt, kann mit dem erfindungsgemässen Ca-AI-Silikat auch ein Reinigungsmittel ohne Abrasivstoffe hergestellt werden. Man erhält dann ein verdicktes, thixotropes, vorzugsweise chlorhaltiges Reinigungsmittel mit nur äusserst schwacher Abrasivwirkung. Im Vergleich zu herkömmlichen abrasivstofffreien chlorhaltigen Flüssigreinigern hat ein derartiges Produkt den Vorteil, an senkrechten Flächen besser zu haften, was sich auf die Güte des Bleicheffektes positiv auswirkt. Derartige Mittel sind beispielsweise aus der DE-A-2810187 bekannt.Although the actual use of the present invention lies in the suspension stabilization of abrasives with grain sizes up to 200 μm in liquid abrasives, a cleaning agent without abrasives can also be produced with the Ca-AI silicate according to the invention. A thickened, thixotropic, preferably chlorine-containing cleaning agent is then obtained with only an extremely weak abrasive effect. Compared to conventional abrasive-free chlorine-containing liquid cleaners, such a product has the advantage of adhering better to vertical surfaces, which has a positive effect on the quality of the bleaching effect. Such agents are known for example from DE-A-2810187.
Die einzelnen Komponenten der beanspruchten Scheuermittel lassen sich wie folgt charakterisieren:
- Als Tenside kommen alle für den Einsatz in Reinigungsmitteln bekannten üblichen anionischen und/oder nichtionischen Verbindungen in Betracht.
- a) Als chlorstabile Tenside kommen z. B. C$-C22-, vorzugsweise C10-C18-Alkansulfonate, Cg-Ci5-, vorzugsweise C10-C13-Alkylbenzolsulfonate, Cf-C18-, vorzugsweise C12-C16-Alkylsulfate, Betaine- und C10-C18-Alkyldimethyl-aminoxide in Frage. Bevorzugt wird eine Mischung aus einem der genannten anionischen Tenside, insbesondere aus einem Alkansulfonat und einem Aminoxid, da derartige Mischungen in Gegenwart von Chlorbleichlauge bereits leicht viskose Lösungen bilden. Diese geringe Viskosität wirkt sich auf die Suspensionsstabilität der fertigen flüssigen chlorhaltigen Scheuermittel zusätzlich positiv aus, reicht jedoch keinesfalls allein aus, um die Abrasivstoffe ohne das erfindungsgemässe weitere Stabilisierungssystem in homogener Verteilung zu halten. Die gleiche vorteilhafte geringe Eigenviskosität einzelner Tensidkomponenten kann erreicht werden, wenn man ihnen geringe Mengen an bekannten Verdickungsmitteln vom Typ der Acrylat- bzw. Methacrylat-Copolymeren zusetzt.
- b) Bekannte, in wässriger Lösung Hypochlorit bildende Aktivchlorverbindungen sind Na-, Li und Ca-Hypochlorit sowie organische Chlorträger wie Chloramin T und chlorierte Isocyanurate. Bevorzugt werden handelsübliche Chlorbleichlaugen mit einem Aktivchlor-Gehalt von 12-16 Gew.-%.
- c) Als Abrasivstoffe können je nach gewünschter Scheuerwirkung solche mit relativ weichem Korn wie Marmormehl, Kieselgure und ähnliche oder solche mit hartem Korn wie Perlit-, Quarz-oder Cristobalitmehle eingesetzt werden. Eine Bevorzugung eines bestimmten Minerals ist nicht gegeben, jedoch muss es alkali- und gegebenenfalls chlorstabil sein, und es muss sichergestellt sein, dass die auf natürliche Fundstellen zurückgehenden Mineralmehle gegebenenfalls nur so geringe Mengen an Verunreinigungen enthalten, dass diese keine katalytische Zersetzung von Chlorbleichlauge fördern. Die Korngrösse richtet sich nach der gewünschten Scheuerleistung. Das Kornspektrum kann zwischen 1 bis 200 11m liegen. Für flüssige Scheuermittel, die für allgemeine Reinigungsaufgaben im Haushalt bestimmt sind, eignet sich besonders ein Kornspektrum von 1 bis 100 µm.
- d) Das in situ zu fällende Ca-AI-Silikat kann aus preiswerten Rohstoffen erzeugt werden, die allerdings ebenfalls weitgehend frei von Schwermetallen und organischen Verunreinigungen sein müssen. Vorteilhaft geht man von den Rohstoffen Calciumchlorid, Aluminiumhydroxid und Wasserglas aus. Die Ausgangsstoffe werden in solchen Mengenverhältnissen untereinander eingesetzt, dass die Molverhältnisse von CaO:Al203:Si02 im Ansatz 1:1:2 betragen.
- e) Die Auswahl von Farb- und Duftstoffen muss sich gegebenenfalls nach deren Beständigkeit in hypochlorithaltiger Lösung richten. Geeignete Farbstoffe sind dann zum Beispiel Cu-Phthalocyanine oder Ultramarinblau. Geeignete Duftstoffe werden beispielsweise in der US-A-3876551 beschrieben.
- Suitable surfactants are all customary anionic and / or nonionic compounds known for use in cleaning agents.
- a) As chlorine-stable surfactants such. B. C $ -C 22 -, preferably C 10 -C 18 alkanesulfonates, Cg-C i5 -, preferably C 10 -C 13 alkylbenzenesulfonates, C f -C 18 -, preferably C 12 -C 16 alkyl sulfates, betaines - And C 10 -C 18 alkyl dimethyl amine oxides in question. A mixture of one of the anionic surfactants mentioned, in particular of an alkane sulfonate and an amine oxide, is preferred, since such mixtures already form slightly viscous solutions in the presence of chlorine bleach. This low viscosity additionally has a positive effect on the suspension stability of the finished liquid chlorine-containing abrasives, but is by no means sufficient to keep the abrasives in a homogeneous distribution without the further stabilization system according to the invention. The same advantageous low inherent viscosity of individual surfactant components can be achieved if small amounts of known thickeners of the acrylate or methacrylate copolymer type are added to them.
- b) Known active chlorine compounds which form hypochlorite in aqueous solution are Na, Li and Ca hypochlorite and also organic chlorine carriers such as chloramine T and chlorinated isocyanurates. Commercial chlorine bleaches with an active chlorine content of 12-16% by weight are preferred.
- c) Depending on the desired abrasive effect, those with relatively soft grain such as marble powder, diatomaceous earth and the like or those with hard grain such as pearlite, quartz or cristobalite powder can be used as abrasives. There is no preference for a particular mineral, but it must be stable to alkali and possibly chlorine, and it must be ensured that mineral flours attributed to natural sources may contain only small amounts of impurities that do not promote the catalytic decomposition of chlorine bleach. The grain size depends on the desired abrasion performance. The grain spectrum can be between 1 to 200 11m. For liquid abrasives that are intended for general household cleaning tasks, a grain size range of 1 to 100 µm is particularly suitable.
- d) The Ca-AI silicate to be precipitated in situ can be produced from inexpensive raw materials, which, however, must also be largely free of heavy metals and organic impurities. The raw materials calcium chloride, aluminum hydroxide and water glass are advantageous. The starting materials are used in such proportions that the molar ratios of CaO: Al 2 0 3 : Si0 2 in the batch are 1: 1: 2.
- e) The selection of colors and fragrances may have to be based on their resistance in hypochlorite-containing solution. Suitable dyes are then, for example, Cu phthalocyanines or ultramarine blue. Suitable fragrances are described for example in US-A-3876551.
Die erfindungsgemässen Reinigungsmittel sind opake, weisse Suspensionen, die sich auch nach längerer Lagerung entweder gar nicht oder nur so schwach trennen, dass sie durch leichtes Schütteln vor Gebrauch wieder homogenisierbar sind.The cleaning agents according to the invention are opaque, white suspensions which, even after prolonged storage, either do not separate at all or only so weakly that they can be homogenized again by gently shaking them before use.
Die Anwendung der beanspruchten Mittel erfolgt durch Herausdrücken aus weichen Plastikflaschen oder Tuben.The claimed agents are applied by pushing them out of soft plastic bottles or tubes.
Zusammensetzung in Gew.-%:
- 6% Dimethyl-Kokosalkyl-aminoxid, 30% Aktivsubstanz, 4% sek.-Alkansulfonat, -Na-Salz, C11-C15, 60% Aktivsubstanz, 5% Chlorbleichlauge, 12-16% Aktivchlor, 25% Calciumcarbonat, Korngrösse 1-100 µm, 8,3% in situ gefälltes Calcium-Aluminium-Silikat, 0,01 % Cu-Phthalocyanin-Farbstoff, 0,2% Parfümöl, Rest Wasser, vollentsalzt.
- 6% dimethyl-cocoalkylamine oxide, 30% active substance, 4% sec-alkanesulfonate, -Na salt, C 11 -C 15 , 60% active substance, 5% chlorine bleach, 12-16% active chlorine, 25% calcium carbonate, grain size 1 -100 µm, 8.3% calcium aluminum silicate precipitated in situ, 0.01% Cu phthalocyanine dye, 0.2% perfume oil, remainder water, fully desalinated.
Nach dem ebenfalls beanspruchten Herstellungsverfahren der erfindungsgemässen Mittel wurde hier wie folgt vorgegangen:
- Zuerst wurden folgende drei Lösungen bereitgestellt:
- I. Aluminatlösung, hergestellt aus 19,7 Gew.-% Hydrargillit, technische Qualität, 88% AI (OH)3, 53,6 Gew.-% NaOH-Lösung, 50%ig und 26,7 Gew.-% Wasser, vollentsalzt
- II. CaC12-Lösung, hergestellt aus 24 Gew.-% CaCl3-6 H2O und 76 Gew.-% Wasser, vollentsalzt und
- 111. Natronwasserglas, 34,5%ig, Molverhältnis SiO2:Na2O = 3,85.
- First three solutions were provided:
- I. aluminate solution, prepared from 19.7% by weight of hydrargillite, technical quality, 88% Al (OH) 3 , 53.6% by weight of NaOH solution, 50% and 26.7% by weight of water, fully desalinated
- II. CaC1 2 solution, made from 24 wt .-% CaCl 3 -6 H 2 O and 76 wt .-% water, fully desalinated and
- 111. Soda water glass, 34.5%, SiO 2 : Na 2 O molar ratio = 3.85.
Dann wurden die Tenside, der Abrasivstoff und der Farbstoff bei Raumtemperatur in Wasser eingerührt. In diese homogene Suspension wurden unter ständigem Rühren sukzessive 10 Gew.-% Lösung II, 10 Gew.-% Lösung I, 5 Gew.-% Lösung III sowie die Chlorlauge und das Parfümöl zugefügt.Then the surfactants, the abrasive and the dye were stirred into water at room temperature. 10% by weight of solution II, 10% by weight of solution I, 5% by weight of solution III as well as the chlorine solution and the perfume oil were added successively to this homogeneous suspension.
Das erhaltene flüssige Scheuermittel war thixotrop, besass eine relativ milde Abrasivwirkung und eine sehr gute Bleichwirkung. Nach ¼ Jahr Lagerung bei Raumtemperatur war die Suspension unverändert und der Chlorverlust betrug nur ca. 22%.The liquid abrasive obtained was thixotropic, had a relatively mild abrasive action and a very good bleaching action. After ¼ year storage at room temperature, the suspension was unchanged and the chlorine loss was only about 22%.
Ohne Zusatz von in situ gefälltem Ca-AI-Silikat und ohne Zusatz sonstiger Stabilisatoren setzte sich der Abrasivstoff nach kurzer Lagerung ab, liess sich zwar aufschütteln, setzte sich aber bald wieder ab. Das Endprodukt war also für eine kommerzielle Verwendung völlig uninteressant.Without the addition of Ca-AI silicate precipitated in situ and without the addition of other stabilizers, the abrasive settled out after a short storage period, could be shaken up, but soon settled again. The end product was therefore completely uninteresting for commercial use.
Entsprechendes galt, wenn anstelle dieses Ca-AI-Silikats handelsüblicher Hectorit (Na-Mg-Silikat) zugesetzt wurde.The same applied if commercial hectorite (Na-Mg silicate) was added instead of this Ca-Al silicate.
Besonders überraschend war auch, dass ein separat frisch gefälltes Ca-AI-Silikat bei der nachträglichen Vereinigung mit der Suspension der übrigen Scheuermittelbestandteile ebenfalls zu einer kurzfristigen Phasentrennung führte.It was also particularly surprising that a separately freshly precipitated Ca-AI silicate, when subsequently combined with the suspension of the other abrasive components, also led to a short-term phase separation.
2% Na-Alkylbenzolsulfonat, C10-C13, 6% Aminoxid, 30%ig, wie Beispiel 1, 0,5% Chloramin T, 10% expandierter Perlit, mittlerer Teilchendurchmesser 7 µm, 5,6% in situ gefälltes Ca-AI-Silikat, Rest Wasser, vollentsalzt.2% Na-alkylbenzenesulfonate, C 10 -C 13 , 6% amine oxide, 30% as in example 1, 0.5% chloramine T, 10% expanded perlite, average particle diameter 7 µm, 5.6% in situ precipitated Ca Al silicate, remainder water, fully desalinated.
Die Herstellung erfolgte analog Beispiel 1. Es handelte sich um eine thixotrope Scheuerpaste mit schwacher Abrasivwirkung. Nach 3 Monaten Lagerung war die Suspension unverändert homogen. Der Aktivchlorgehalt war praktisch erhalten geblieben.The preparation was carried out analogously to Example 1. It was a thixotropic abrasive paste with a weak abrasive effect. After 3 months of storage, the suspension remained homogeneous. The active chlorine content was practically retained.
4% Alkansulfonat-Na-Salz, 60%ig, wie Beispiel 1, 6% Dimethyl-Kokosalkyl-aminoxid, 30%ig, 5% Chlorbleichlauge, 12-16% Aktivchlor, 25% Cristobalit-Mehl, Korngrösse 1-100 µm, 8,3% in situ gefälltes Ca-AI-Silikat, 0,1 % Duftstoff, Rest Wasser, vollentsalzt.4% alkanesulfonate Na salt, 60%, as in Example 1, 6% dimethyl-cocoalkylamine oxide, 30%, 5% chlorine bleach, 12-16% active chlorine, 25% cristobalite flour, particle size 1-100 µm, 8.3% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.
Die Herstellung erfolgte analog Beispiel 1.The preparation was carried out analogously to Example 1.
Es handelte sich um ein flüssiges Scheuermittel mit kräftiger Abrasivwirkung. Sowohl hinsichtlich der Suspensions- als auch der Chlorstabilität war es gut lagerfähig. Der Aktivchlorverlust nach 3 mon betrug ca. 24%.It was a liquid abrasive with a strong abrasive effect. It was easy to store in terms of both suspension and chlorine stability. The active chlorine loss after 3 months was approx. 24%.
2% Alkansulfonat-Na-Salz, 60%ig, wie Beispiel 1, 3% Aminoxid, 30%ig, wie Beispiel 1, 5% Chlorbleichlauge, 12-16% Aktivchlor, 25% Marmormehl, Korngrösse 1-100 µm, 13% in situ gefälltes Ca-AI-Silikat, 0,1 % Duftstoff, Rest Wasser, vollentsalzt.2% alkanesulfonate Na salt, 60%, as in Example 1, 3% amine oxide, 30%, as in Example 1, 5% chlorine bleach, 12-16% active chlorine, 25% marble powder, grain size 1-100 µm, 13% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.
Die Herstellung erfolgte ebenfalls analog Beispiel 1.The preparation was also carried out analogously to Example 1.
Das flüssige Scheuermittel hatte ähnlich gute Eigenschaften wie das nach Beispiel 1 hergestellte; der Aktivchlorverlust nach 3 mon Lagerzeit bei Raumtemperatur betrug nur etwa 20%.The liquid abrasive had properties similar to those of Example 1; the active chlorine loss after 3 months' storage at room temperature was only about 20%.
4,0% Alkansulfonat-Na-Salz, 60%ig, wie Beispiel 1, 6,0% Aminoxid, wie Beispiel 1, 5,0% Chlorbleichlauge, 12-16% Aktivchlor, 45,0% Marmormehl, mittlerer Teilchendurchmesser 15 µm, 5,6% in situ gefälltes Ca-AI-Silikat, 0,2% Duftstoff, Rest Wasser, vollentsalzt.4.0% alkanesulfonate Na salt, 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% chlorine bleach, 12-16% active chlorine, 45.0% marble powder, average particle diameter 15 μm , 5.6% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.
Die Herstellung erfolgte analog Beispiel 1.The preparation was carried out analogously to Example 1.
Es handelte sich um eine Scheuerpaste mit mittlerer Abrasivwirkung und guter Lagerstabilität, auch in bezug auf den Aktivchlorgehalt. Nach 3 mon bei Raumtemperatur lag der Chlorverlust bei etwa 27 %.It was a scouring paste with a medium abrasive effect and good storage stability, also with regard to the active chlorine content. After 3 months at room temperature, the chlorine loss was about 27%.
4,0% Alkansulfonat-Na-Salz, 60%ig, wie Beispiel 1, 6,0% Aminoxid, wie Beispiel 1, 5,0% Chlorbleichlauge, 12-16% Aktivchlor, 13,0% in situ gefälltes Ca-AI-Silikat, 0,2% Duftstoff, Rest Wasser, vollentsalzt.4.0% alkanesulfonate Na salt, 60%, as in Example 1, 6.0% amine oxide, as in Example 1, 5.0% Chlorine bleach, 12-16% active chlorine, 13.0% Ca-AI silicate precipitated in situ, 0.2% fragrance, remainder water, fully desalinated.
Die Herstellung dieses abrasivstoffreien, aktivchlorhaltigen verdickten Reinigungsmittels erfolgte ebenfalls analog Beispiel 1. Diese Paste, die gut auch an senkrechten Flächen haftete, war auch nach 6 mon Lagerzeit bei Raumtemperatur noch homogen und der Chlorverlust lag unter 50%.This abrasive-free, active chlorine-containing thickened cleaning agent was also produced analogously to Example 1. This paste, which also adhered well to vertical surfaces, was still homogeneous even after 6 months of storage at room temperature and the chlorine loss was less than 50%.
2,5% Alkansulfonat-Na-Salz, 60%ig, wie Beispiel 1, 2,0% Aminoxid, wie Beispiel 1, 40,0% Marmormehl, Korngrösse 1-100 µm, 5,0% in situ gefälltes Ca-AI-Silikat, 0,2% Duftstoff, 0,2% Formaldehyd, 30%ig, Rest Wasser, vollentsalzt. Die Herstellung dieses abrasivstoffhaltigen, aktivchlorfreien Scheuermittels erfolgte entsprechend den Aufgaben in Beispiel 1, jedoch wurde hier wegen des Fehlens der Aktivchlorverbindung bei der Fällung des Calcium-Aluminium-Silikats vor der Zugabe von Wasserglas durch langsames Hinzufügen von verdünnter Salzsäure auf einen pH-Wert von etwa 10 eingestellt. Die Suspension war nach 3 mon noch stabil.2.5% alkanesulfonate Na salt, 60%, as in Example 1, 2.0% amine oxide, as in Example 1, 40.0% marble powder, grain size 1-100 μm, 5.0% Ca-AI precipitated in situ -Silicate, 0.2% fragrance, 0.2% formaldehyde, 30%, the rest water, fully desalinated. This abrasive-containing, active chlorine-free scouring agent was produced in accordance with the tasks in Example 1, but because of the lack of the active chlorine compound in the precipitation of the calcium aluminum silicate, before adding water glass, it was brought to a pH of approximately by slowly adding dilute hydrochloric acid 10 set. The suspension was still stable after 3 months.
8% sek.-Alkansulfonat, C11-C15, Na-Salz, 60% Aktivsubstanz, 2% Methacryl-Ethylacrylat-Copolymer, 20%ige wässrige Dispersion, 5% Chlorbleichlauge, 12-16% Aktivchlor, 45% Marmormehl, mittlerer Teilchendurchmesser 15 µm, 5% in situ gefälltes Ca-AI-Silikat, 0,1 % Duftstoff, Rest Wasser, vollentsalzt.8% sec-alkanesulfonate, C 11 -C 15 , Na salt, 60% active substance, 2% methacrylic ethyl acrylate copolymer, 20% aqueous dispersion, 5% chlorine bleach, 12-16% active chlorine, 45% marble powder, medium Particle diameter 15 µm, 5% Ca-AI silicate precipitated in situ, 0.1% fragrance, remainder water, fully desalinated.
Die Herstellung erfolgte analog Beispiel 1, das Copolymere wurde im Anschluss an das Marmormehl zugefügt. Vor der Wasserglaszugabe wurde mit verdünnter Salzsäure ein pH-Wert von 12,5 eingestellt, der sich nach Fertigstellung des flüssigen Scheuermittels nicht mehr veränderte.The preparation was carried out analogously to Example 1, the copolymer was added after the marble powder. Before adding the water glass, a pH of 12.5 was set with dilute hydrochloric acid, which did not change after the liquid abrasive was finished.
Das giessfähige, bleichende Scheuermittel zeigte sowohl in bezug auf die Suspensions- als auch auf die Chlorstabilität ähnlich gute Lagerergebnisse wie die vorgenannten Beispiele.The pourable, bleaching abrasive showed similarly good storage results to both the suspension stability and the chlorine stability as the aforementioned examples.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83110508T ATE22701T1 (en) | 1982-10-29 | 1983-10-21 | STABLE AQUEOUS CLEANING AGENTS AND PROCESSES FOR THEIR MANUFACTURE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19823240088 DE3240088A1 (en) | 1982-10-29 | 1982-10-29 | STABLE AQUEOUS DETERGENT AND METHOD FOR THE PRODUCTION THEREOF |
DE3240088 | 1982-10-29 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0110106A2 EP0110106A2 (en) | 1984-06-13 |
EP0110106A3 EP0110106A3 (en) | 1985-03-13 |
EP0110106B1 true EP0110106B1 (en) | 1986-10-08 |
Family
ID=6176902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83110508A Expired EP0110106B1 (en) | 1982-10-29 | 1983-10-21 | Stable, aqueous detergents and process for their preparation |
Country Status (8)
Country | Link |
---|---|
US (1) | US4438016A (en) |
EP (1) | EP0110106B1 (en) |
JP (1) | JPS5993798A (en) |
AT (1) | ATE22701T1 (en) |
BR (1) | BR8305972A (en) |
DE (2) | DE3240088A1 (en) |
ES (1) | ES526823A0 (en) |
ZA (1) | ZA838077B (en) |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5920396A (en) * | 1982-07-27 | 1984-02-02 | 花王株式会社 | Liquid detergent composition |
MX167884B (en) * | 1983-12-22 | 1993-04-20 | Albright & Wilson | LIQUID DETERGENT COMPOSITION |
US4599186A (en) * | 1984-04-20 | 1986-07-08 | The Clorox Company | Thickened aqueous abrasive scouring cleanser |
US4751016A (en) * | 1985-02-26 | 1988-06-14 | The Clorox Company | Liquid aqueous abrasive cleanser |
JPH064874B2 (en) * | 1985-05-16 | 1994-01-19 | 花王株式会社 | Colored cleaning composition |
GB8515720D0 (en) * | 1985-06-21 | 1985-07-24 | Unilever Plc | Detergent compositions |
JPS62273297A (en) * | 1986-05-20 | 1987-11-27 | 栗島 良江 | Detergent |
JPS62285999A (en) * | 1986-06-02 | 1987-12-11 | マツダ株式会社 | Fungicidal agent on film |
EP0287514A1 (en) * | 1987-04-15 | 1988-10-19 | Ciba-Geigy Ag | Detergent for the after treatment of fiber reactive dyeings, process for its preparation and its use |
US4789495A (en) * | 1987-05-18 | 1988-12-06 | The Drackett Company | Hypochlorite compositions containing a tertiary alcohol |
NZ224700A (en) * | 1987-05-26 | 1991-09-25 | Bristol Myers Co | Aqueous cleaner comprising alkali metal halogenite, perfume and an anionic surfactant stabiliser |
US4842757A (en) * | 1988-01-21 | 1989-06-27 | The Clorox Company | Thickened liquid, improved stability abrasive cleanser |
US5346641A (en) * | 1992-01-17 | 1994-09-13 | The Clorox Company | Thickened aqueous abrasive cleanser with improved colloidal stability |
GB2305434B (en) * | 1995-09-19 | 1999-03-10 | Reckitt & Colmann Sa | Abrasive cleaning composition |
US6010539A (en) * | 1996-04-01 | 2000-01-04 | E. I. Du Pont De Nemours And Company | Cleaning formulations for textile fabrics |
US5731276A (en) * | 1996-07-30 | 1998-03-24 | The Clorox Company | Thickened aqueous cleaning composition and methods of preparation thereof and cleaning therewith |
EP0922082B1 (en) * | 1996-08-16 | 2003-05-14 | E.I. Du Pont De Nemours And Company | Fabric cleaning formulations |
DE19646520A1 (en) * | 1996-11-12 | 1998-05-14 | Henkel Kgaa | Dishwashing detergent with increased cleaning effect |
CA2332305A1 (en) | 1998-06-09 | 1999-12-16 | Luciano Novita | Hard surface cleaners |
US8680031B1 (en) * | 2012-03-19 | 2014-03-25 | Roanoke College | Exfoliating compositions comprising a ternary mixture of inorganic exfoliants |
AU2017352302B2 (en) | 2016-10-26 | 2020-09-10 | Elc Management Llc | Delayed release delivery systems and methods |
CA3041897A1 (en) | 2016-10-26 | 2018-05-03 | Elc Management Llc | Delayed release delivery systems and methods |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3755180A (en) * | 1972-02-25 | 1973-08-28 | Colgate Palmolive Co | Means to inhibit overglaze damage by automatic dishwashing detergents |
US4248728A (en) * | 1979-02-28 | 1981-02-03 | Chemed Corporation | Liquid scouring cleanser |
-
1982
- 1982-10-29 DE DE19823240088 patent/DE3240088A1/en not_active Withdrawn
-
1983
- 1983-03-16 US US06/475,869 patent/US4438016A/en not_active Expired - Lifetime
- 1983-10-21 EP EP83110508A patent/EP0110106B1/en not_active Expired
- 1983-10-21 DE DE8383110508T patent/DE3366706D1/en not_active Expired
- 1983-10-21 AT AT83110508T patent/ATE22701T1/en not_active IP Right Cessation
- 1983-10-27 JP JP58200129A patent/JPS5993798A/en active Granted
- 1983-10-27 ES ES526823A patent/ES526823A0/en active Granted
- 1983-10-27 BR BR8305972A patent/BR8305972A/en not_active IP Right Cessation
- 1983-10-28 ZA ZA838077A patent/ZA838077B/en unknown
Also Published As
Publication number | Publication date |
---|---|
ES8501795A1 (en) | 1984-12-01 |
US4438016A (en) | 1984-03-20 |
ES526823A0 (en) | 1984-12-01 |
EP0110106A3 (en) | 1985-03-13 |
ATE22701T1 (en) | 1986-10-15 |
JPS5993798A (en) | 1984-05-30 |
BR8305972A (en) | 1984-06-05 |
ZA838077B (en) | 1984-07-25 |
DE3240088A1 (en) | 1984-05-03 |
EP0110106A2 (en) | 1984-06-13 |
DE3366706D1 (en) | 1986-11-13 |
JPH0455240B2 (en) | 1992-09-02 |
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