EP0326795B1 - Use of polyglycol ethers as anti-foaming agents in detergents - Google Patents
Use of polyglycol ethers as anti-foaming agents in detergents 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
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- 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.
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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)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Die Erfindung betrifft die Verwendung ausgewählter Endgruppen-verschlossener Polyethylenglykolether als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln. Die Erfindung will dabei Hilfsmittel der genannten Art zur Verfügung stellen, die hohe Wirksamkeit mit physiologischer Unbedenklichkeit und biologischer Abbaubarkeit vereinigen. Die neuen Hilfsmittel der Erfindung sollen insbesondere auch dazu geeignet sein, bei stark schaumerzeugenden Reinigungsprozessen, beispielsweise bei der Spritzreinigung, im Bereich niedriger Temperaturen, insbesondere im Bereich der Raumtemperatur oder nur schwach erhöhter Temperaturen, wirkungsvoll eine unerwünschte Schaumbildung zu unterdrücken.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.
Für die Verwendung in Gewerbe und Industrie bestimmte wäßrige Reinigungsmittel, insbesondere solche für die Reinigung von Metall-, Glas- und Keramikoberflächen, enthalten in der Regel Substanzen, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzuwirken. Der Einsatz von schaumdrückenden Zusätzen ist in den meisten Fällen dadurch bedingt, daß die von den Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken. Daneben kann die Verwendung von Antischaummitteln auch aufgrund der Tatsache erforderlich sein, daß die Reinigungsmittel selbst Bestandteile enthalten, die unter den vorgegebenen Arbeitsbedingungen zu unerwünschter Schaumbildung Anlaß geben. Ein Beispiel hierfür sind die in Reinigungsmitteln in weitem Umfang eingesetzten Aniontenside.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. In most cases, the use of 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. In addition, the use of 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. An example of this are the anionic surfactants widely used in cleaning agents.
Als schaumdrückende Zusätze werden seit langem Anlagerungsprodukte von Alkylenoxiden an organische Verbindungen mit reaktiven Wasserstoffatomen im Molekül eingesetzt. Hier haben sich insbesondere Anlagerungsprodukte von Propylenoxid an aliphatische Polyalkohole - siehe beispielsweise DE-PS 1 280 455 und DE-PS 1 621 592 - und an aliphatische Polyamine - vergleiche beispielsweise DE-PS 1 289 597 und DE-PS 1 621 593 - sowie Anlagerungsprodukte von Ethylenoxid und Propylenoxid an aliphatische Polyamine, insbesondere Ethylendiamin - vergleiche DE-PS 1 944 569 - in der Praxis bewährt. Diese Alkylenoxidanlagerungsprodukte besitzen neben einer guten schaumdrückenden Wirkung auch die für die Anwendung in gewerblichen und industriellen Reinigungsmitteln zumeist erforderliche Alkalistabilität. Die Verbindungen dieser Klasse sind jedoch nicht hinreichend biologisch abbaubar, um den geltenden gesetzlichen Vorschriften zu genügen.Addition products of alkylene oxides with organic compounds with reactive hydrogen atoms in the molecule have long been used as foam-suppressing additives. Here, in particular, 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. In addition to having a good foam-suppressing effect, these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents. However, the compounds in this class are not sufficiently biodegradable to meet the applicable legal requirements.
Eine Klasse hochwirksamer und gleichzeitig biologisch abbaubarer Entschäumungshilfsmittel ist in der DE-OS 33 15 951 beschrieben. Geschildert wird dort die Verwendung von Endgruppen-verschlossenen Polyethylenglykolethern der Formel (I) R₁O-(CH₂CH₂O)n-R₂, wobei in dieser Formel R₁ einen geradkettigen oder verzweigten Alkylrest oder Alkenylrest mit 8 bis 18 Kohlenstoffatomen, R₂ einen Alkylrest mit 4 bis 8 Kohlenstoffatomen und n eine Zahl von 7 bis 12 bedeuten. In der Praxis besonders bewährt hat sich ein Produkt dieser Art, in der der Rest R₁ einen Fettalkoholrest mit 12 bis 18 Kohlenstoffatomen und R₂ den n-Butylrest bedeuten, wobei n für die Zahl 10 steht.A class of highly effective and at the same time biodegradable defoaming agents is described in DE-OS 33 15 951. Described there is the use of end-capped polyethylene glycol ethers of the formula (I) R₁O- (CH₂CH₂O) n -R₂, in which formula R₁ is a straight-chain or branched alkyl radical or alkenyl radical with 8 to 18 carbon atoms, R₂ is an alkyl radical with 4 to 8 carbon atoms and n is a number from 7 to 12. A product of this type in which the radical R 1 is a fatty alcohol radical having 12 to 18 carbon atoms and R 2 is the n-butyl radical, in which n stands for the number 10, has proven particularly useful in practice.
Die Europäische Patentanmeldung EP-A-0 322 781 betrifft ein Verfahren zur Herstellung einer Vielzahl von Mischethern, die einen linearen oder verzweigten C₁-C₂₀-Alkylrest (R¹), Wasserstoff oder einen linearen oder verzweigten, aliphatischen, araliphatischen oder aromatischen Kohlenwasserstoffrest mit 0 bis 19 Kohlenstoffatomen (R²) sowie 2 bis 50 Ethylenglycol- und 0 bis 10 Propylenglycoleinheiten (n) aufweisen. Gemäß der Offenbarung auf Seite 3, Zeilen 29 bis 30 ist bekannt, daß sich Verbindungen dieses Typs grundsätzlich als schaumdrückende Zusätze in schaumarmen Reinigungsmitteln eignen. Welche Species für diesen Zweck besonders geeignet sind, wird hingegen nicht erwähnt.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. According to the disclosure on page 3, lines 29 to 30, it is known that compounds of this type are suitable in principle as foam-suppressing additives in low-foam cleaning agents. However, no mention is made of which species are particularly suitable for this purpose.
Die Deutsche Patentanmeldung DE-A 25 56 544 betrifft Maschinengeschirrspülmittel mit einem Gehalt an Mischethern, bei denen R¹ für lineare oder verzweigte Alkyl- oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R² für einen tert.Butylrest und n für 5 bis 50 Ethylenglycol- bzw. Propylenglycoleinheiten steht. Gemäß der Offenbarung auf Seite 4, letzter Absatz werden solche Mischether als besonders vorteilhaft erachtet, bei denen R¹ für einen linearen Alkylrest mit 8 bis 14 Kohlenstoffatomen steht.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. According to the disclosure on page 4, last paragraph, such mixed ethers are considered to be particularly advantageous in which R 1 is a linear alkyl radical having 8 to 14 carbon atoms.
Gegenstand der US 3,684,723 sind schließlich Waschmittel, enthaltend anionische Tenside, Buildersalze, Seifen und schaumregulierende nichtionische Tenside vom Mischethertyp, die einen sehr niedrigen HLB-Wert im Bereich von 1 bis 4 aufweisen.Finally, 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.
Die Lehre der vorliegenden Erfindung geht von der überraschenden Erkenntnis aus, daß man noch wirkungsvollere Hilfsmittel der hier betroffenen Art dadurch erhalten kann, daß die zuletzt erwähnten Endgruppen-verschlossenen Fettalkoholpolyethylenglykolether in ihrer Struktur leicht variiert werden. Im Sinne des erfindungsgemäßen Handelns ist es dabei nicht nur möglich, eine allgemeine Wirkungssteigerung unter Erhalt der physiologischen Unbedenklichkeit und biologischen Abbaubarkeit dieser schaumdrückenden Zusatzstoffe einzustellen, mit den jetzt beschriebenen variierten Ethylenglykolethern erschließt sich insbesondere ein verbessertes Arbeiten im niedrigeren Temperaturbereich, beispielsweise also im Bereich der Raumtemperatur oder nur schwach erhöhter Temperaturen.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. In the sense of the action according to the invention, it is not only possible to set a general increase in activity while maintaining the physiological harmlessness and biodegradability of these foam-suppressing additives, with the now varied ethylene glycol ethers, in particular improved working in the lower temperature range, for example in the area of the room temperature or only slightly elevated temperatures.
Hier liegt gegenüber den vorbekannten schaumdrückenden Zusätzen eine sehr wichtige Erweiterung. Es ist bekannt, daß in gewerblichen Reinigungsprozessen häufig Spülprozesse gerade bei niedrigen Temperaturen durchgeführt werden sollen, um beispielsweise eine energiesparende Vorreinigung durchzuführen. Konventionelle, schaumdrückende Zusatzstoffe zeichnen sich häufig dadurch aus, daß sie im Temperaturbereich von etwa 50 °C und darüber sehr wirkungsvoll der Schaumbekämpfung dienen, ihr Einsatz bei Temperaturen von etwa 20 °C führt aber zu einer vergleichsweise schwächeren Schaumdämpfung. Überraschenderweise zeigt sich, daß die im nachfolgenden beschriebenen erfindungsgemäßen Zusatzstoffe gerade bei niedrigeren Temperaturen besondere Wirksamkeit entfalten und diese Eigenschaft auch dann zeigen, wenn sie mit strukturähnlichen, vorbekannten Komponenten verschnitten werden.This is a very important extension compared to the known foam-suppressing additives. It is known that in industrial cleaning processes, rinsing processes 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. Surprisingly, it has been found that 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.
Gegenstand der Erfindung ist dementsprechend die Verwendung von Polyethylenglykolethern der allgemeinen Formel (I)
R₁O-(CH₂CH₂O)n-R₂ (I)
in der
- R₁
- einen verzweigten Alkyl rest mit 20 bis 24 C-Atomen,
- R₂
- einen n-Butylrest und
- n
- eine Zahl von 6 bis 12 bedeuten,
R₁O- (CH₂CH₂O) n -R₂ (I)
in the
- R₁
- a branched alkyl radical with 20 to 24 carbon atoms,
- R₂
- an n-butyl radical and
- n
- represent a number from 6 to 12,
Die entscheidende Abwandlung der erfindungsgemäßen Polyethylenglykolether der allgemeinen Formel (I) gegenüber den strukturähnlichen Verbindungen der zuvor genannten DE-OS 33 15 951 liegt in der Variation des Restes R₁. Erfindungsgemäß ist die Kohlenstoffzahl dieses Restes gegenüber den vorbeschriebenen Resten erhöht, und liegt bei wenigstens 20 C-Atomen. Fettalkohole natürlichen Ursprungs dieser Art sind in an sich bekannter Weise durch Hydrierung der oberen Schnitte natürlicher Fettsäuregemische bzw. der daraus gewonnenen Methylester zu erhalten. Insbesondere wird durch die Erfindung jedoch die Klasse der Guerbet-Alkohole betroffen. Alkohole dieser Art entstehen bekanntlich durch Kondensation von Fettalkoholen niedrigerer Kohlenstoffzahl in Gegenwart von Alkali, z.B. Kaliumhydroxid oder Kaliumalkoholat. Die Reaktion läuft beispielsweise bei Temperaturen von 200 bis 300 °C ab und führt zu verzweigten Guerbet-Alkoholen, die die Verzweigung in 2-Stellung zur Hydroxylgruppe aufweisen. Zur Synthese können ausgewählte Fettalkohole oder auch Gemische verschiedener Fettalkohole eingesetzt werden, entsprechend komplex zusammengesetzt ist dann das entstehende Alkoholgemisch höherer Kohlenstoffzahl.The decisive modification of the polyethylene glycol ether of the general formula (I) according to the invention compared to the structure-like compounds of the aforementioned DE-OS 33 15 951 lies in the variation of the radical R 1. According to the invention, 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. In particular, however, the class of Guerbet alcohols is affected by the invention. As is known, 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.
Als Ausgangsmaterial für die Herstellung der Polyglykolether der Formel (I) können beispielsweise 2-Octyldodecanol-1 und 2-Decyl-tetradecanol-1 sowie ihre Gemische eingesetzt werden.For example, 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).
Die Herstellung der Endgruppen-verschlossenen Fettalkoholpolyglykolether der Formel (I) erfolgt entsprechend den Angaben der DE-OS 33 15 951. So setzt man zweckmäßigerweise die vorstehend beschriebenen Fettalkohole höherer Kohlenstoffzahl mit Ethylenoxid im Molverhältnis von 1 : 6 bis 1 : 20 um und verethert anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxylierungsbedingungen, vorzugweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamsonschen Ethersynthese mit n-Butyl halogeniden durchgeführt. Beispiel für eine solche abschließende Veretherung ist dementsprechend n-Butyliodid. Die Erfindung ist allerdings hierauf nicht beschränkt.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. However, the invention is not limited to this.
Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkali im stöchiometrischen Überschuß, beispielsweise von 10 bis 50 %, über die zu verethernden Hydroxylgruppen einzusetzen.It may be expedient to use a stoichiometric excess of alkyl halide and alkali, for example from 10 to 50%, use the hydroxyl groups to be etherified.
Die erfindungsgemäß zu verwendenden Endgruppen-verschlossenen Polyglykolether der Formel (I) werden in einer wichtigen Ausführungsform in Abmischung mit strukturgleichen Polyethylenglykolethern eingesetzt, in denen jedoch der Rest R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 8 bis 18 C-Atomen bedeutet und n eine Zahl von 7 bis 12, und bevorzugt von 8 bis 10 ist. In dieser Ausführungsform sieht damit die Erfindung vor, die hier neu beschriebenen, im Rest R₁ längerkettigen Polyglykolether mit den schaumdrückenden Zusatzstoffen aus der DE-OS 33 15 951 zu verschneiden. Geeignet sind für diese Ausführungsform Mischungsverhältnisse der beiden Typen im Bereich von 10 bis 90 zu 90 bis 10 Gew.-%, insbesondere in Gewichtsverhältnissen von 60 bis 40 zu 40 bis 60 Gew.-%.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. In this embodiment, 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.
Auch die erfindungsgemäß jetzt zu verwendenden Endgruppenverschlossenen Polyglykolether der Formel (I) zeichnen sich durch eine hohe Alkali- und Säurestabilität aus. Ihre schaumverhindernde Wirkung in alkalischen und neutralen Reinigungsflotten ist im angegebenen Sinne verstärkt, darüberhinaus erfüllen sie die gesetzlichen Anforderungen an die biologische Abbaubarkeit.The 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.
Die Reinigungsmittel, in denen die Endgruppen-verschlossenen Polyglykolether der Erfindung zur Anwendung kommen, können die in solchen Mitteln üblichen Bestandteile wie Netzmittel, Gerüstsubstanzen und Komplexbildner, Alkalien oder Säuren, Korrosionsinhibitoren und gegebenenfalls auch organische Lösungsmittel enthalten. Als Netzmittel kommen nichtionogene oberflächenaktive Verbindungen wie Polyglykolether, die durch Anlagerung von Ethylenoxid an Alkohole, insbesondere Fettalkohole, Alkylphenole, Fettamine und Carbonsäureamide erhalten werden, sowie anionaktive Netzmittel wie Alkalimetall-, Amin-und Alkylolaminsalze von Fettsäuren, Alkylschwefelsäuren, Alkylsulfonsäuren und Alkylbenzolsulfonsäuren in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polymerphosphate, -silikate, -borate, -carbonate, -polyacrylate und -glukonate sowie Citronensäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure, 1-Hydroxyalkan-1,1-diphosphonsäuren und Ethylendiamintetra-(methylenphosphonsäure), Phosphonoalkanpolycarbonsäuren wie z.B. Phosphonobutantricarbonsäure und Alkalimetallsalze dieser Säuren enthalten. Hochalkalische Reinigungsmittel, insbesondere solche für die Flaschenreinigung, enthalten beträchtliche Mengen Ätzalkali in Form von Natrium- und/oder Kaliumhydroxid. Wenn besondere Reinigungseffekte gewünscht werden, können die Reinigungsmittel organische Lösungsmittel, beispielsweise Alkohole, Benzinfraktionen und chlorierte Kohlenwasserstoffe sowie freie Alkylolamine enthalten.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. On builders and complexing agents, 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. If special cleaning effects are desired, the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons as well as free alkylolamines.
Unter Reinigungsmitteln werden im Zusammenhang mit der Erfindung einmal die zur direkten Anwendung auf die zu reinigenden Substrate bestimmten wäßrigen Lösungen verstanden, daneben umfaßt der Begriff Reinigungsmittel aber auch die zur Herstellung der Anwendungslösungen bestimmten Konzentrate und festen Mischungen.In connection with the invention, 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.
Die gebrauchsfertigen Lösungen können sauer bis stark alkalisch sein; sie werden in der Regel bei Temperaturen von etwa 20 bis 90 °C eingesetzt.The ready-to-use solutions can be acidic to strongly alkaline; they are generally used at temperatures of around 20 to 90 ° C.
Die erfindungsgemäß zu verwendenden Endgruppen-verschlossenen Polyglykolether geben bereits in geringen Konzentrationen wirkungsvolle Effekte. Bevorzugt werden sie den Reinigungsmitteln in solchen Mengen zugesetzt, daß ihre Konzentration in den gebrauchsfertigen Lösungen etwa im Bereich von 50 bis 500 ppm liegt.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.
In den nachfolgenden Beispielen wird die Schaumdämpfung der erfindungsgemäß ausgewählten Zusatzstoffe - und im Vergleich dazu strukturähnlicher jedoch nicht in den Rahmen der Erfindung fallender Zusatzstoffe - nach einer Prüfmethode ermittelt, die wie folgt beschrieben wird:
In einem doppelwandigen 2 l-Meßzylinder werden 300 ml einer 1 %igen wäßrigen Natronlauge auf 20 bzw. 65 °C temperiert. Anschließend wird der jeweils ausgewählte schaumdrückende Zusatzstoff in den nachfolgend angegebenen Mengen zugesetzt. Mit Hilfe einer Laborschlauchpumpe wird die Flüssigkeit mit einer Umwälzgeschwindigkeit von 4 l pro Minute umgepumpt. Dabei wird die Prüflösung ca. 5 mm über den Boden des Meßzylinders mittels eines 55 cm langen Glasrohres (Innendurchmesser 8,5 mm, Außendurchmesser 11 mm), das mit der Pumpe über einen Silikonschlauch verbunden ist, angesaugt und über ein zweites Glasrohr (Länge 20 cm), das an der 2000 ml-Marke angebracht ist, in freiem Fall zurückgeführt.In the following examples, 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. 5 mm above the bottom of the measuring cylinder by means of a 55 cm long glass tube (inner diameter 8.5 mm, outer diameter 11 mm), which is connected to the pump via a silicone hose, and through a second glass tube (length 20 cm) attached to the 2000 ml mark in free fall.
Nach 30 Sekunden dosiert man zunächst 1 ml einer 1 %-igen wäßrigen Lösung des Triethanolaminsalzes von Tetrapropylenbenzolsulfonat (in den nachfolgenden Tabellen als "Testschäumer" bezeichnet) in die Flotte und bestimmt nach weiteren 30 Sekunden das entstandene Volumen, das durch Flüssigkeit und Schaum gebildet wird. In Zeitabständen von jeweils 1 Minute wird nachfolgend weiterer Testschäumer jeweils in Portionen von 1 ml zudosiert und das nach 30 Sekunden entstandene Volumen aus Flüssigkeit und Schaum bestimmt. Diesen stufenweisen Zyklus von Zudosierung des Testschäumers und Volumenbestimmung nach 30 Sekunden behält man so lange bei, bis die Tensidlösung im Meßzylinder auf 2000 ml aufgeschäumt ist.After 30 seconds, first 1 ml of a 1% aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate (referred to in the tables below as "test foamer") is added to the liquor and after a further 30 seconds the volume formed, which is formed by liquid and foam, is determined . At intervals of 1 minute each, further test foamers are then metered in in portions of 1 ml and the volume of liquid and foam formed after 30 seconds is determined. This step-by-step cycle of metering in the test foamer and determining the volume after 30 seconds is maintained until the surfactant solution in the measuring cylinder is foamed to 2000 ml.
Es wird ein erfindungsgemäß ausgewählter schaumdrückender Zusatzstoff A jeweils bei 20 °C und 65 °C eingesetzt und dabei seine schaumdrückende Wirkung mit einem Zusatzstoff des Standes der Technik (Produkt B) verglichen. Die schaumdrückenden Zusatzstoffe A und B werden dabei in der angegebenen Prüfmethode jeweils in Mengen von 0,1 ml der reinen Substanz verwendet.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.
Dem eingesetzten Produkt A und B sind dabei die folgenden:The products A and B used are the following:
Die in den Vergleichsversuchen bestimmten Werte sind in der nachfolgenden Tabelle 1 zusammengefaßt.
Nach der angebebenen Prüfmethode werden 2 Flaschenreinigerformulierungen der nachfolgend in Tabelle 2 angegebenen Zusammensetzung untersucht. Die erste der beiden Rezepturen enthält dabei als schaumdrückenden Zusatzstoff ausschließlich das zuvor genannte Produkt B des Standes der Technik. Die zweite Rezeptur verwendet im Sinne des erfindungsgemäßen Handelns ein Gemisch des schaumdrückenden Zusatzstoffs A in Abmischung mit dem Produkt B nach dem Stand der Technik.According to 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.
Die nachfolgende Tabelle 2 faßt die abgelesenen Werte zusammen. Sie zeigt darüberhinaus einen weiteren Vorteil für die erfindungsgemäße Lehre:
Die Flaschenreinigerrezeptur gemäß der Erfindung ist auch noch bei Temperaturen unterhalb 0 °C als Flüssigphase lagerstabil.
The bottle cleaner formulation according to the invention is also stable in storage as a liquid phase at temperatures below 0 ° C.
Claims (3)
- The use of polyethylene glycol ethers corresponding to general formula (I):
R¹O-(CH₂CH₂O) n -R² (I)
in which R¹ is a branched alkyl radical containing 20 to 24 carbon atoms, R² is an n-butyl radical and n is a number of 6 to 12,
as foam-suppressing additives for low-foaming cleaning preparations. - The use claimed in claim 1, characterized in that the polyglycol ethers corresponding to general formula (I) are used in admixture with polyethylene glycol ethers of the same structure except that R¹ is a linear or branched alkyl or alkenyl radical containing 8 to 18 carbon atoms and n is a number of 7 to 12.
- The use claimed in claim 1, characterized in that the polyethylene glycol ethers corresponding to general formula (I) are used in such quantities that their concentration in the ready-to-use solutions is approximately 50 to 500 ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3800493A DE3800493A1 (en) | 1988-01-11 | 1988-01-11 | USE OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS, IN PARTICULAR ALSO SUITABLE FOR COLD CLEANING |
| DE3800493 | 1988-01-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0326795A2 EP0326795A2 (en) | 1989-08-09 |
| EP0326795A3 EP0326795A3 (en) | 1990-08-22 |
| EP0326795B1 true EP0326795B1 (en) | 1994-08-17 |
Family
ID=6345046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89100009A Expired - Lifetime EP0326795B1 (en) | 1988-01-11 | 1989-01-02 | Use of polyglycol ethers as anti-foaming agents in detergents |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4954283A (en) |
| EP (1) | EP0326795B1 (en) |
| JP (1) | JPH01215894A (en) |
| AT (1) | ATE110105T1 (en) |
| BR (1) | BR8900095A (en) |
| CA (1) | CA1327932C (en) |
| DE (2) | DE3800493A1 (en) |
| DK (1) | DK1589A (en) |
| ES (1) | ES2056957T3 (en) |
| TR (1) | TR24792A (en) |
| ZA (1) | ZA89197B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3928604A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | USE OF SELECTED MIXTURES OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM DETERGENTS |
| DE3928603A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING |
| DE3928600A1 (en) | 1989-08-30 | 1991-03-07 | Henkel Kgaa | FOAM-ABSORBING MULTI-MATERIAL MIXTURES WITH TENSIDE CHARACTER FOR MACHINE CLEANING AND BOTTLE CLEANING |
| DE3928602A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | ALKALISTABLE AND STRONG ALKALINE-MOLDABLE ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING |
| US5612305A (en) * | 1995-01-12 | 1997-03-18 | Huntsman Petrochemical Corporation | Mixed surfactant systems for low foam applications |
| DE19959311A1 (en) | 1999-12-09 | 2001-08-23 | Henkel Ecolab Gmbh & Co Ohg | Defoamer preparation and its use |
| KR20030011349A (en) | 2000-06-05 | 2003-02-07 | 에스.씨. 존슨 앤드 선, 인코포레이티드 | Biocidal cleaner composition |
| JP2011021266A (en) * | 2009-07-21 | 2011-02-03 | Hakko Sangyo Kk | Cleaning liquid for gl heat exchanger and method for cleaning gl heat exchanger by using the same |
| FR3000086B1 (en) * | 2012-12-20 | 2014-12-26 | Coatex Sas | AGENT FOR OBTAINING A STABLE AQUEOUS COMPOSITION COMPRISING SUSPENDED PARTICLES |
| EP2968092B1 (en) * | 2013-03-15 | 2020-05-27 | Croda, Inc. | Alkoxylated fatty alcohol alkyl ethers and products containing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0322781A2 (en) * | 1987-12-30 | 1989-07-05 | Henkel Kommanditgesellschaft auf Aktien | Use of end-capped polyglycolethers |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK126125A (en) * | 1964-04-21 | |||
| DE2556544A1 (en) * | 1975-12-16 | 1977-06-30 | Hoechst Ag | Detergent for dish washing machine - contains alkali-stable, low-foam nonionic polyglycol tert. butyl ether |
| DE3315951A1 (en) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
| DE3315952A1 (en) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
| DE3345349A1 (en) * | 1983-12-15 | 1985-06-27 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
| EP0197434B1 (en) * | 1985-04-03 | 1989-07-19 | Henkel Kommanditgesellschaft auf Aktien | Rinsing agents for use in mechanical dish washing |
| DE3531212A1 (en) * | 1985-08-31 | 1987-03-05 | Henkel Kgaa | ALKYLENE OXIDE BLOCK POLYMERS TO BE USED AS A DEFOAMER |
| US4836951A (en) * | 1986-02-19 | 1989-06-06 | Union Carbide Corporation | Random polyether foam control agents |
| DE3773781D1 (en) * | 1986-07-24 | 1991-11-21 | Henkel Kgaa | LOW-FOAM AND / OR FOAM-ABSORBING SURFACTANT MIXTURES AND THEIR USE. |
-
1988
- 1988-01-11 DE DE3800493A patent/DE3800493A1/en not_active Withdrawn
-
1989
- 1989-01-02 AT AT89100009T patent/ATE110105T1/en not_active IP Right Cessation
- 1989-01-02 ES ES89100009T patent/ES2056957T3/en not_active Expired - Lifetime
- 1989-01-02 EP EP89100009A patent/EP0326795B1/en not_active Expired - Lifetime
- 1989-01-02 DE DE58908196T patent/DE58908196D1/en not_active Expired - Fee Related
- 1989-01-03 DK DK001589A patent/DK1589A/en not_active Application Discontinuation
- 1989-01-10 BR BR898900095A patent/BR8900095A/en unknown
- 1989-01-10 TR TR89/0047A patent/TR24792A/en unknown
- 1989-01-10 ZA ZA89197A patent/ZA89197B/en unknown
- 1989-01-11 JP JP1005855A patent/JPH01215894A/en active Pending
- 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
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0322781A2 (en) * | 1987-12-30 | 1989-07-05 | Henkel Kommanditgesellschaft auf Aktien | Use of end-capped polyglycolethers |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1327932C (en) | 1994-03-22 |
| DK1589A (en) | 1989-07-12 |
| ZA89197B (en) | 1990-08-29 |
| EP0326795A2 (en) | 1989-08-09 |
| DK1589D0 (en) | 1989-01-03 |
| EP0326795A3 (en) | 1990-08-22 |
| US4954283A (en) | 1990-09-04 |
| ATE110105T1 (en) | 1994-09-15 |
| DE3800493A1 (en) | 1989-07-20 |
| BR8900095A (en) | 1989-09-05 |
| TR24792A (en) | 1992-03-10 |
| JPH01215894A (en) | 1989-08-29 |
| ES2056957T3 (en) | 1994-10-16 |
| DE58908196D1 (en) | 1994-09-22 |
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