EP0326795B1 - Verwendung von Polyglykolethern als schaumvermindernde Zusätze für Reinigungsmittel - Google Patents
Verwendung von Polyglykolethern als schaumvermindernde Zusätze für Reinigungsmittel Download PDFInfo
- Publication number
- EP0326795B1 EP0326795B1 EP89100009A EP89100009A EP0326795B1 EP 0326795 B1 EP0326795 B1 EP 0326795B1 EP 89100009 A EP89100009 A EP 89100009A EP 89100009 A EP89100009 A EP 89100009A EP 0326795 B1 EP0326795 B1 EP 0326795B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- polyethylene glycol
- radical
- polyglycol ethers
- glycol ethers
- 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
- 150000002170 ethers Chemical class 0.000 title claims abstract description 22
- 229920000151 polyglycol Polymers 0.000 title claims description 10
- 239000010695 polyglycol Substances 0.000 title claims description 10
- 239000002518 antifoaming agent Substances 0.000 title description 3
- 239000003599 detergent Substances 0.000 title description 3
- 239000000654 additive Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 alkyl radical Chemical class 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 abstract description 15
- 239000006260 foam Substances 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 150000002191 fatty alcohols Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IIVWHGMLFGNMOW-UHFFFAOYSA-N 2-methylpropane Chemical compound C[C](C)C IIVWHGMLFGNMOW-UHFFFAOYSA-N 0.000 description 1
- 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
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- FODHIQQNHOPUKH-UHFFFAOYSA-N tetrapropylene-benzenesulfonic acid Chemical compound CC1CC11C2=C3S(=O)(=O)OC(C)CC3=C3C(C)CC3=C2C1C FODHIQQNHOPUKH-UHFFFAOYSA-N 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
Definitions
- the invention relates to the use of selected end group-sealed polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.
- the invention aims to provide tools of the type mentioned which combine high effectiveness with physiological harmlessness and biodegradability.
- the new auxiliaries of the invention should in particular also be suitable for effectively suppressing undesirable foam formation in the case of strongly foam-generating cleaning processes, for example spray cleaning, in the range of low temperatures, in particular in the range of room temperature or only slightly elevated temperatures.
- Aqueous cleaning agents intended for use in trade and industry in particular those for cleaning metal, glass and ceramic surfaces, generally contain substances which are able to counteract undesirable foam development.
- foam-suppressing additives is due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents.
- anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves Contain components that give rise to undesirable foaming under the specified working conditions.
- anionic surfactants widely used in cleaning agents.
- Addition products of alkylene oxides with organic compounds with reactive hydrogen atoms in the molecule have long been used as foam-suppressing additives.
- addition products of propylene oxide onto aliphatic polyalcohols - see, for example, DE-PS 1 280 455 and DE-PS 1 621 592 - and onto aliphatic polyamines - compare, for example, DE-PS 1 289 597 and DE-PS 1 621 593 - and addition products of ethylene oxide and propylene oxide to aliphatic polyamines, especially ethylenediamine - compare DE-PS 1 944 569 - proven in practice.
- these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents.
- the compounds in this class are not sufficiently biodegradable to meet the applicable legal requirements.
- the European patent application EP-A-0 322 781 relates to a process for the preparation of a large number of mixed ethers which have a linear or branched C1-C20alkyl radical (R1), hydrogen or a linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
- R1-C20alkyl radical R1
- R2 linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
- R1-C20alkyl radical R1
- R2 linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
- German patent application DE-A 25 56 544 relates to machine dishwashing detergents containing mixed ethers in which R1 for linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, R2 for a tert-butyl radical and n for 5 to 50 ethylene glycol or Propylene glycol units.
- mixed ethers are considered to be particularly advantageous in which R 1 is a linear alkyl radical having 8 to 14 carbon atoms.
- US Pat. No. 3,684,723 relates to detergents containing anionic surfactants, builder salts, soaps and foam-regulating nonionic surfactants of the mixed ether type, which have a very low HLB value in the range from 1 to 4.
- the teaching of the present invention is based on the surprising finding that even more effective auxiliaries of the type concerned here can be obtained by slightly varying the structure of the last-mentioned end group-sealed fatty alcohol polyethylene glycol ethers.
- foam-suppressing additives are often to be carried out at low temperatures, for example in order to carry out an energy-saving pre-cleaning.
- Conventional, foam-suppressing additives are often characterized by the fact that they are very effective in combating foam in the temperature range of approximately 50 ° C. and above, but their use at temperatures of approximately 20 ° C. leads to comparatively weaker foam damping.
- the additives according to the invention described below develop particular effectiveness precisely at lower temperatures and also exhibit this property when they are blended with structurally similar, known components.
- the carbon number of this radical is increased compared to the radicals described above, and is at least 20 carbon atoms.
- Fatty alcohols of natural origin of this type can be obtained in a manner known per se by hydrogenating the upper sections of natural fatty acid mixtures or the methyl esters obtained therefrom.
- the class of Guerbet alcohols is affected by the invention.
- alcohols of this type are formed by the condensation of fatty alcohols with a lower carbon number in the presence of alkali, for example potassium hydroxide or potassium alcoholate.
- the reaction takes place, for example, at temperatures of 200 to 300 ° C and leads to branched Guerbet alcohols, which branch in the 2-position to the hydroxyl group.
- Selected fatty alcohols or also mixtures of different fatty alcohols can be used for the synthesis; the resulting alcohol mixture with a higher carbon number is of correspondingly complex composition.
- 2-octyldodecanol-1 and 2-decyl-tetradecanol-1 and their mixtures can be used as the starting material for the preparation of the polyglycol ethers of the formula (I).
- the end group-capped fatty alcohol polyglycol ethers of the formula (I) are produced in accordance with the specifications of DE-OS 33 15 951.
- the fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 6 to 1:20 and then etherified the hydroxyl groups present in the reaction product obtained.
- the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts.
- the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with n-butyl halides. Accordingly, an example of such a final etherification is n-butyl iodide.
- the invention is not limited to this.
- alkyl halide and alkali for example from 10 to 50%, use the hydroxyl groups to be etherified.
- the end group-capped polyglycol ethers of the formula (I) to be used according to the invention are used in an important embodiment in a mixture with structurally identical polyethylene glycol ethers, but in which the radical R 1 is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 C atoms and n is one Number is from 7 to 12, and preferably from 8 to 10.
- the invention thus provides to blend the newly described here, longer R1 long-chain polyglycol ethers with the foam-suppressing additives from DE-OS 33 15 951.
- Mixing ratios of the two types in the range from 10 to 90 to 90 to 10% by weight, in particular in weight ratios from 60 to 40 to 40 to 60% by weight, are suitable for this embodiment.
- end group-capped polyglycol ethers of the formula (I) which are now to be used according to the invention are also notable for high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is strengthened in the specified sense, moreover they also meet the legal requirements for biodegradability.
- the cleaning agents in which the end-group-capped polyglycol ethers of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, and corrosion inhibitors and optionally also contain organic solvents.
- Suitable wetting agents are nonionic surface-active compounds such as polyglycol ethers, which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic wetting agents such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids.
- the cleaning agents can, above all, alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane-1,1-diphosphonic acid and ethylenediphosphonic acid, Contain phosphonoalkane polycarboxylic acids such as phosphonobutane tricarboxylic acid and alkali metal salts of these acids.
- Highly alkaline cleaning agents especially those for bottle cleaning, contain considerable amounts of caustic alkali in the form of sodium and / or potassium hydroxide.
- the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons as well as free alkylolamines.
- cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrates to be cleaned, but the term cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.
- the ready-to-use solutions can be acidic to strongly alkaline; they are generally used at temperatures of around 20 to 90 ° C.
- the end group-sealed polyglycol ethers to be used according to the invention give effective effects even in low concentrations. They are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use solutions is approximately in the range from 50 to 500 ppm.
- the foam attenuation of the additives selected according to the invention - and, in comparison, structurally similar additives but not within the scope of the invention - is determined using a test method which is described as follows: 300 ml of a 1% aqueous sodium hydroxide solution are heated to 20 or 65 ° C. in a double-walled 2 l measuring cylinder. The selected foam-suppressing additive is then added in the amounts specified below. With the help of a laboratory hose pump, the liquid is pumped around at a circulation rate of 4 l per minute. The test solution is sucked in approx.
- test foamer a 1% aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate
- test foamer 1 ml of a 1% aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate
- a foam-suppressing additive A selected according to the invention is used in each case at 20 ° C. and 65 ° C. and its foam-suppressing effect is compared with an additive of the prior art (product B).
- the foam-suppressing additives A and B are used in the test method specified in amounts of 0.1 ml of the pure substance.
- the products A and B used are the following:
- Table 1 ml test foamer Product A Product B 20 ° C 65 ° C 20 ° C 65 ° C 0 300 300 400 300 1 300 300 460 320 2nd 300 300 580 340 3rd 300 300 680 360 4th 340 300 800 400 5 380 300 1000 420 6 400 320 1400 440 7 420 400 1600 460 8th 420 460 1820 540 9 460 520 2000 780 10th 480 620 940 11 500 760 1240 12th 540 860 1760 13 580 1000 1880 14 600 1100 1940 15 660 1220 2000 16 720 1480 17th 800 1620 18th 1000 1760 19th 1300 1860 20th 1680 2000 21 2000
- the test method specified 2 bottle cleaner formulations with the composition given in Table 2 below are examined.
- the first of the two formulations contains only the previously mentioned product B of the prior art as a foam-suppressing additive.
- the second recipe uses a mixture of the foam-suppressing additive A in admixture with the product B according to the prior art in the sense of the inventive action.
- the bottle cleaner formulation according to the invention is also stable in storage as a liquid phase at temperatures below 0 ° C.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3800493A DE3800493A1 (de) | 1988-01-11 | 1988-01-11 | Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln, die insbesondere auch fuer die kaltreinigung geeignet sind |
DE3800493 | 1988-01-11 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0326795A2 EP0326795A2 (de) | 1989-08-09 |
EP0326795A3 EP0326795A3 (en) | 1990-08-22 |
EP0326795B1 true EP0326795B1 (de) | 1994-08-17 |
Family
ID=6345046
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89100009A Expired - Lifetime EP0326795B1 (de) | 1988-01-11 | 1989-01-02 | Verwendung von Polyglykolethern als schaumvermindernde Zusätze für Reinigungsmittel |
Country Status (11)
Country | Link |
---|---|
US (1) | US4954283A (pt) |
EP (1) | EP0326795B1 (pt) |
JP (1) | JPH01215894A (pt) |
AT (1) | ATE110105T1 (pt) |
BR (1) | BR8900095A (pt) |
CA (1) | CA1327932C (pt) |
DE (2) | DE3800493A1 (pt) |
DK (1) | DK1589A (pt) |
ES (1) | ES2056957T3 (pt) |
TR (1) | TR24792A (pt) |
ZA (1) | ZA89197B (pt) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3928602A1 (de) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | Alkalistabile und stark alkalisch formulierbare antischaummittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung |
DE3928603A1 (de) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | Antischaumittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung |
DE3928604A1 (de) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | Verwendung ausgewaehlter gemische von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln |
DE3928600A1 (de) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | Schaumdaempfende mehrstoffgemische mit tensidcharakter fuer die maschinelle geschirr- und flaschenreinigung |
US5612305A (en) * | 1995-01-12 | 1997-03-18 | Huntsman Petrochemical Corporation | Mixed surfactant systems for low foam applications |
DE19959311A1 (de) | 1999-12-09 | 2001-08-23 | Henkel Ecolab Gmbh & Co Ohg | Entschäumerzubereitung und deren Verwendung |
DE60124906T2 (de) | 2000-06-05 | 2007-05-24 | S.C. Johnson & Son, Inc., Racine | Biozide reinigungsmittel |
JP2011021266A (ja) * | 2009-07-21 | 2011-02-03 | Hakko Sangyo Kk | Gl熱交換器用洗浄液とそれを用いたgl熱交換器の洗浄方法 |
FR3000086B1 (fr) * | 2012-12-20 | 2014-12-26 | Coatex Sas | Agent pour obtenir une composition aqueuse stable comprenant des particules en suspension |
JP6591960B2 (ja) * | 2013-03-15 | 2019-10-16 | クローダ,インコーポレイティド | アルコキシ化脂肪族アルコールアルキルエーテル、及びそれを含有する製品 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0322781A2 (de) * | 1987-12-30 | 1989-07-05 | Henkel Kommanditgesellschaft auf Aktien | Verwendung engruppenverschlossener Polyglycolether |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK126125A (pt) * | 1964-04-21 | |||
DE2556544A1 (de) * | 1975-12-16 | 1977-06-30 | Hoechst Ag | Maschinengeschirrspuelmittel |
DE3315952A1 (de) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln |
DE3315951A1 (de) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln |
DE3345349A1 (de) * | 1983-12-15 | 1985-06-27 | Henkel KGaA, 4000 Düsseldorf | Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln |
DE3664480D1 (en) * | 1985-04-03 | 1989-08-24 | Henkel Kgaa | Rinsing agents for use in mechanical dish washing |
DE3531212A1 (de) * | 1985-08-31 | 1987-03-05 | Henkel Kgaa | Als entschaeumer verwendbare alkylenoxid-blockpolymere |
US4836951A (en) * | 1986-02-19 | 1989-06-06 | Union Carbide Corporation | Random polyether foam control agents |
DE3773781D1 (de) * | 1986-07-24 | 1991-11-21 | Henkel Kgaa | Schaumarme und/oder schaumdaempfende tensidgemische und ihre verwendung. |
-
1988
- 1988-01-11 DE DE3800493A patent/DE3800493A1/de not_active Withdrawn
-
1989
- 1989-01-02 ES ES89100009T patent/ES2056957T3/es not_active Expired - Lifetime
- 1989-01-02 DE DE58908196T patent/DE58908196D1/de not_active Expired - Fee Related
- 1989-01-02 AT AT89100009T patent/ATE110105T1/de not_active IP Right Cessation
- 1989-01-02 EP EP89100009A patent/EP0326795B1/de not_active Expired - Lifetime
- 1989-01-03 DK DK001589A patent/DK1589A/da not_active Application Discontinuation
- 1989-01-10 TR TR89/0047A patent/TR24792A/xx unknown
- 1989-01-10 BR BR898900095A patent/BR8900095A/pt unknown
- 1989-01-10 ZA ZA89197A patent/ZA89197B/xx unknown
- 1989-01-11 CA CA000587981A patent/CA1327932C/en not_active Expired - Lifetime
- 1989-01-11 US US07/295,872 patent/US4954283A/en not_active Expired - Lifetime
- 1989-01-11 JP JP1005855A patent/JPH01215894A/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0322781A2 (de) * | 1987-12-30 | 1989-07-05 | Henkel Kommanditgesellschaft auf Aktien | Verwendung engruppenverschlossener Polyglycolether |
Also Published As
Publication number | Publication date |
---|---|
DE3800493A1 (de) | 1989-07-20 |
ZA89197B (en) | 1990-08-29 |
EP0326795A3 (en) | 1990-08-22 |
ES2056957T3 (es) | 1994-10-16 |
JPH01215894A (ja) | 1989-08-29 |
US4954283A (en) | 1990-09-04 |
DK1589D0 (da) | 1989-01-03 |
EP0326795A2 (de) | 1989-08-09 |
DK1589A (da) | 1989-07-12 |
TR24792A (tr) | 1992-03-10 |
ATE110105T1 (de) | 1994-09-15 |
DE58908196D1 (de) | 1994-09-22 |
CA1327932C (en) | 1994-03-22 |
BR8900095A (pt) | 1989-09-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0489777B1 (de) | Alkalistabile antischaummittel | |
EP0254208B1 (de) | Schaumarme und/oder schaumdämpfende Tensidgemische und ihre Verwendung | |
EP0303928B1 (de) | Schaumdrückende Zusätze in schaumarmen Reinigungsmitteln | |
EP0124815B1 (de) | Verwendung von Polyglykolethern als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln | |
DE1956671C3 (de) | Grenzflächenaktives Mittel | |
EP0197434B1 (de) | Klarspülmittel für die maschinelle Geschirreinigung | |
EP0675942B1 (de) | Netzmittel für die textile vorbehandlung | |
EP0161537A2 (de) | Endgruppenverschlossene Fettalkoholalkoxylate für industrielle Reinigungsprozesse, insbesondere für die Flaschenwäsche und für die Metallreinigung | |
EP0415988A1 (de) | Schaumdrückende alkylpolyglykolether für reinigungsmittel (i) | |
EP0054894B1 (de) | Tensidhaltiges Gemisch zur Reinigung harter Oberflächen | |
EP0326795B1 (de) | Verwendung von Polyglykolethern als schaumvermindernde Zusätze für Reinigungsmittel | |
EP0146854A2 (de) | Verwendung von Polyglykolethern als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln | |
EP0489768B1 (de) | Antischaummittel für die maschinelle geschirr- und flaschenreinigung | |
EP0126967A1 (de) | Verwendung von Polyglykolethern als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln | |
DE1289597B (de) | Hochalkalische, lagerstabile und schaumarme Flaschenreinigungsmittel | |
DE3928601A1 (de) | Verwendung ausgewaehlter mischungen von polyalkylendiolethern als schaumdrueckende zusaetze fuer schaumarme reinigungsmittel | |
EP0694606B1 (de) | Mischungen von Alkoxylaten als schaumdämpfendes Mittel und deren Verwendung | |
EP0489769B1 (de) | Verwendung von polyglykolethergemischen als antischaummittel | |
EP0040343B1 (de) | Farbstabilisierte, nichtionische Tenside und ihre Verwendung als Wirksubstanzen in Wasch- und Reinigungsmitteln | |
EP0343504A1 (de) | Schaumdrückende Alkylpolyglykolether für Reinigungsmittel | |
EP0564402B1 (de) | Schaumarme oberflächenaktive Verbindungen | |
CH629846A5 (de) | Klarspuelmittel fuer die maschinelle geschirreinigung. | |
WO1991003539A1 (de) | Antischaummittel für die gewerbliche reinigung | |
DE1161375B (de) | Waschmittel, insbesondere fuer Geschirrwaschmaschinen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19900906 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
17Q | First examination report despatched |
Effective date: 19930426 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 110105 Country of ref document: AT Date of ref document: 19940915 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 58908196 Country of ref document: DE Date of ref document: 19940922 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2056957 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: FG4A Free format text: 3012982 |
|
ITF | It: translation for a ep patent filed | ||
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19941125 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 19950125 Year of fee payment: 7 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 89100009.3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19951219 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19951220 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19960119 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19960124 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19960130 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19960212 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19960731 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: MM2A Free format text: 3012982 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Effective date: 19970102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19970103 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19970131 Ref country code: CH Effective date: 19970131 Ref country code: BE Effective date: 19970131 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 19970131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970801 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970801 |
|
EUG | Se: european patent has lapsed |
Ref document number: 89100009.3 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19971224 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980109 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980112 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990102 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19990405 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19990102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991103 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050102 |