EP0489777B1 - Anti-foaming agents stable in alkali - Google Patents
Anti-foaming agents stable in alkali Download PDFInfo
- Publication number
- EP0489777B1 EP0489777B1 EP90912683A EP90912683A EP0489777B1 EP 0489777 B1 EP0489777 B1 EP 0489777B1 EP 90912683 A EP90912683 A EP 90912683A EP 90912683 A EP90912683 A EP 90912683A EP 0489777 B1 EP0489777 B1 EP 0489777B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- mol
- general formula
- decanol
- hexyl
- 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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- 239000003513 alkali Substances 0.000 title claims description 10
- 239000002518 antifoaming agent Substances 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 49
- -1 alkyl glucosides Chemical class 0.000 claims abstract description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- 150000002170 ethers Chemical class 0.000 claims abstract description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 12
- 239000006260 foam Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012141 concentrate Substances 0.000 claims abstract description 9
- 229930182478 glucoside Natural products 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- 238000009472 formulation Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 239000013543 active substance Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229940071118 cumenesulfonate Drugs 0.000 claims description 7
- 229920000151 polyglycol Polymers 0.000 claims description 7
- 239000010695 polyglycol Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229940071104 xylenesulfonate Drugs 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- XULHFMYCBKQGEE-MRXNPFEDSA-N 2-Hexyl-1-decanol Natural products CCCCCCCC[C@H](CO)CCCCCC XULHFMYCBKQGEE-MRXNPFEDSA-N 0.000 claims 4
- XULHFMYCBKQGEE-UHFFFAOYSA-N 2-hexyl-1-Decanol Chemical compound CCCCCCCCC(CO)CCCCCC XULHFMYCBKQGEE-UHFFFAOYSA-N 0.000 claims 4
- LEACJMVNYZDSKR-UHFFFAOYSA-N 2-octyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCCCC LEACJMVNYZDSKR-UHFFFAOYSA-N 0.000 claims 4
- LOIMOHMWAXGSLR-UHFFFAOYSA-N 2-hexyldodecan-1-ol Chemical compound CCCCCCCCCCC(CO)CCCCCC LOIMOHMWAXGSLR-UHFFFAOYSA-N 0.000 claims 3
- JYZLSYFPFQTNNO-UHFFFAOYSA-N 2-octyldecan-1-ol Chemical compound CCCCCCCCC(CO)CCCCCCCC JYZLSYFPFQTNNO-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 claims 2
- QNMCWJOEQBZQHB-UHFFFAOYSA-N 2-Hexyl-1-octanol Chemical compound CCCCCCC(CO)CCCCCC QNMCWJOEQBZQHB-UHFFFAOYSA-N 0.000 claims 1
- FAOVRYZLXQUFRR-UHFFFAOYSA-N 2-butyldecan-1-ol Chemical compound CCCCCCCCC(CO)CCCC FAOVRYZLXQUFRR-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 239000012459 cleaning agent Substances 0.000 abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 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
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
-
- 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
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- 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
- C11D1/662—Carbohydrates or derivatives
-
- 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
-
- 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
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
Definitions
- the invention relates to the use of selected mixtures of end-capped and on the other hand not end-capped polyethylene glycol ethers as alkali-stable and homogeneously formulated foam-suppressing additives in low-foam detergents in aqueous, highly concentrated alkali solutions.
- the active substance mixtures according to the invention are particularly suitable as anti-foaming agents for bottle cleaning and for so-called cleaning-in-place (CIP) cleaning.
- CIP cleaning-in-place
- the invention aims to provide tools of the type mentioned which combine high effectiveness with physiological harmlessness and biodegradability.
- the invention is also based on the object to enable optimization of the performance profile of the auxiliaries used in practical use, on the one hand, but on the other hand to provide selected polyethylene glycol ethers of the type mentioned, which ensures improved formulation of these auxiliaries in commercially available concentrate form.
- foam-suppressing aids is mostly due to the fact that the detached from the substrates and in the cleaning baths accumulating impurities act as foaming agents.
- the cleaning agents themselves can also contain constituents which give rise to undesirable foaming under the given working conditions.
- anionic surfactants are widely used anionic surfactants.
- DE-OS 38 00 493 (D 8113) describes the use of polyethylene glycol ethers of the general formula (I) given above, but now in this formula R 1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 6 to 20.
- R 1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 carbon atoms
- R2 is an alkyl radical with 4 to 8 carbon atoms
- n is a number from 6 to 20.
- the crucial modification here is the use of longer chain residues R 1.
- These end group-capped polyglycol ethers are also characterized by high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is specified in the Strengthens the senses, moreover they also meet the legal requirements for biodegradability.
- nonionic surfactants based on polyglycol ether compounds cannot easily be incorporated into aqueous, strongly alkaline formulations. They easily form a separate phase from the aqueous phase and therefore require the use of solubilizers.
- Known effective solubilizers, especially especially for strongly alkaline cleaning formulations, are alkyl mono- and / or oligoglucosides, which must also be a preferred class of substances in the given context for ecological reasons.
- EP-A2-0 202 638 describes a liquid cleaning concentrate for strongly alkaline cleaning formulations consisting of end group-capped fatty alcohol glycol ether compounds with mixed oligoalkoxide residues together with a combination of three solubilizers which are intended to ensure homogeneous formulation in strongly alkaline aqueous solutions.
- One of these solubilizers used is alkyl mono- and / or alkyl polyglucosides with 8 to 12 carbon atoms in the alkyl radical and 1 to 6 glucose units. Also in US Pat. No.
- an alkaline detergent concentrate for washing bottles is an aqueous concentrate containing 10 to 35% by weight of alkali metal hydroxide, 10 to 50% by weight of a mixture of a polyoxypropylene-polyoxyethylene condensate, an etherified ethoxylated alcohol and one Alkylglucosids described. It is a disadvantage, particularly in the context of this last-mentioned teaching, that these preparations foam too much during practical use, in particular through the use of the alkylglucoside. In addition, phase separations occur at high alkali contents.
- the teaching of the present invention is based on the task, by fine tuning and optimizing the selection of the polyethylene glycol ether compounds used, to obtain mixtures which are distinguished by particularly high-quality effects when used as anti-foaming agents, and this effect optimization both at comparatively low temperatures - So, for example, in the range of about 20 ° C - as well as at the elevated temperatures usually used in practice in the range of about 60 to 70 ° C.
- the invention further aims to enable the formulation of these auxiliaries in strongly alkaline, highly concentrated aqueous solutions to form single-phase systems. This single-phase formulability should be ensured over the temperature range that is essential in practice, for example from about 20 to 70 ° C.
- the teaching of the invention is based on the knowledge that the joint use of two structurally similar but not structurally identical polyethylene glycol compounds in cooperation with the alkyl glucosides leads to the desired optimization if at the same time the constitutional features defined below for the construction of the respective type of polyethylene glycol ether -Connections are observed.
- compounds of the general formula (II) in which the R5O- radical is derived from alkanols or alkanol mixtures which, for determining the R1O- radical, are derived from the general formula ( I) have previously been defined as subclasses (2a), (2b), (2c) and / or (2d).
- compounds of the general formula (II) can also be used here which are derived from 2-butyloctanol-1, 2-butyldecanol-1 and / or 2-hexyloctanol-1 with respect to their radical R5O-.
- the active ingredients or active ingredient mixtures for (2) and (3) of the general formulas (I) and (II) are present together with the alkylglucosides. If desired, the active ingredient components to numbers (4) - d. H. the end group-capped polyethylene glycol ether compounds of the general formula (III) -, alkali metal salts of cumene sulfonate and / or xylene sulfonate and also deionized water.
- the reaction takes place, for example, at temperatures from 200 to 300 ° C. and leads to branched Guerbet alcohols which have branching in the 2 position to the hydroxyl group.
- the invention predominantly or preferably exclusively uses straight-chain fatty alcohols for the preparation of the 2-branched Guerbet alcohols and ultimately for the synthesis of the compounds of the general formula (I). It is known that fatty alcohols of natural origin have at least largely predominantly even chain lengths, so that their 2-branched Guerbet alcohol with 18 C atoms cannot be obtained as a uniform condensation product of only one selected fatty alcohol via their dimerization.
- the necessary dimerization of a mixture of the two fatty alcohols with 8 and 10 C atoms leads to the isomer mixture of the 18 C Guerbet alcohol from 2-hexyldodecanol-1 and 2-octyldecanol-1.
- the condensation products of the two alcohols used arise with themselves, ie the 2-hexyldecanol-1 from the octanol used and the 2-octyldodecanol-1 from the decanol used.
- end group-capped - but also those not capped with end groups - fatty alcohol polyglycol ethers of the formula (I) or of the formula (II) are prepared in accordance with the specifications of DE-OS 33 15 951. This is advantageously done the fatty alcohols of higher carbon number described above with ethylene oxide in a molar ratio of 1: 5 to 1: 9 or 1: 2 to 1: 5 ⁇ m and, if desired, then etherify 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 using straight-chain or branched C4- to C8-alkyl halides.
- the n-butyl radical for the radical R2 from the general formula (I) is of particular importance in the course of the inventive action. Examples of such a final etherification are accordingly n-butyl halides such as n-butyl chloride.
- the invention is not limited to this. Further examples are amyl halides, hexyl halides and the higher alkyl halides in the range mentioned.
- Compounds of the general formula (III) are prepared analogously.
- alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
- the cleaning agents in which the partially end-capped polyglycol ether mixtures of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also organic solvents.
- the surfactants used are non-ionic surface-active compounds of the polyglycol ether type which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consideration.
- alcohols in particular fatty alcohols, alkylphenols, fatty amines and carboxamides
- anionic surfactants such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consideration.
- the cleaning agents can be builders and complexing agents, in particular 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 and ethylene Phosphonoalkane polycarboxylic acids, e.g. B. 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.
- storage-stable active ingredient mixtures which are foamable and preferably liquid in the temperature range from about 20 to 60 ° C. and which, for example, contain 5 to 30% by weight of the active ingredient concentrates from the components ( 1) to (3) and, if desired, additionally (4) to (6) together with 70 to 95% by weight of concentrated aqueous alkali metal hydroxide solutions.
- These alkali hydroxide solutions can be aqueous sodium and / or potassium hydroxide solutions with an alkali hydroxide content of at least 30% by weight, in particular at least 40% by weight.
- Suitable is, for example, aqueous approximately 50% sodium hydroxide solution as the main part of a formulation according to the invention, which is stable in storage up to approximately 70 ° C. as a homogeneously clear aqueous solution.
- polyglycol ether mixtures to be used according to the invention give effective effects even in low concentrations.
- Such detergents are preferred in such quantities added that their concentration in the ready-to-use solutions is approximately in the range of 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:
- the defoaming effect is tested under the following conditions: 300 ml of a 1% strength by weight aqueous sodium hydroxide solution are heated to 20 ° C. or 65 ° C. in a double-walled 2 liter measuring cylinder. 0.1 ml of the defoaming surfactant to be determined is added to this solution. With the help of a peristaltic pump, the liquid is circulated at a rate of 4 l / min. pumped around. The test liquor is approx.
- a 1% by weight aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate is used as the test foam. This is metered in at intervals of one minute in amounts of 1 ml each of the liquor in circulation. The resulting total volume of foam and liquid is determined.
- the foam-inhibiting effect of the surfactant material used in each case is all the better the longer the period of time required to reach the 2000 ml mark in the measuring cylinder due to the total volume of the liquid and foam phases.
- the respective are corresponding Numerical values for this time are given in minutes or in ml of test foamers.
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Abstract
Description
Die Erfindung betrifft die Verwendung ausgewählter Gemische von einerseits Endgruppen-verschlossenen und andererseits nicht mit Endgruppen-verschlossenen Polyethylenglykolethern als alkalistabile und in wäßrigen hochkonzentrierten Alkalilösungen homogen formulierbare schaumdrückende Zusätze in schaumarmen Reinigungsmitteln. Die erfindungsgemäßen Wirkstoffgemische eignen sich insbesondere als Antischaummittel für die Flaschenreinigung und für die sogenannte Cleaning-in-Place-(CIP)-Reinigung. Die Erfindung will dabei Hilfsmittel der genannten Art zur Verfügung stellen, die hohe Wirksamkeit mit physiologischer Unbedenklichkeit und biologischer Abbaubarkeit vereinigen. Die Erfindung geht darüber hinaus von der Aufgabe aus, einerseits eine Optimierung des Leistungsprofils der eingesetzten Hilfsmittel im praktischen Einsatz zu ermöglichen, andererseits aber ausgewählte Polyethylenglykolether der angesprochenen Art zur Verfügung zu stellen, die eine verbesserte Formulierbarkeit dieser Hilfsstoffe in handelsüblicher Konzentratform sicherstellt.The invention relates to the use of selected mixtures of end-capped and on the other hand not end-capped polyethylene glycol ethers as alkali-stable and homogeneously formulated foam-suppressing additives in low-foam detergents in aqueous, highly concentrated alkali solutions. The active substance mixtures according to the invention are particularly suitable as anti-foaming agents for bottle cleaning and for so-called cleaning-in-place (CIP) cleaning. The invention aims to provide tools of the type mentioned which combine high effectiveness with physiological harmlessness and biodegradability. The invention is also based on the object to enable optimization of the performance profile of the auxiliaries used in practical use, on the one hand, but on the other hand to provide selected polyethylene glycol ethers of the type mentioned, which ensures improved formulation of these auxiliaries in commercially available concentrate form.
Schaumarme Reinigungsmittel für die Verwendung in Gewerbe und Industrie, insbesondere für die Reinigung von Metall-, Glas- und Keramik-Oberflächen enthalten im allgemeinen schaumdrückende Zusätze, die in der Lage sind, einer unerwünschten Schaumentwicklung entgegenzuwirken. Diese Mitverwendung der schaumdrückenden Hilfsmittel ist meist dadurch bedingt, daß die von den Substraten abgelösten und in den Reinigungsbädern sich ansammelnden Verunreinigungen als Schaumbildner wirken. Aber auch die Reinigungsmittel selbst können Bestandteile enthalten, die unter den vorgegebenen Arbeitsbedingungen zu unerwünschter Schaumbildung Anlaß geben. Ein Beispiel hierfür sind die in weitem Umfang eingesetzten Aniontenside.Low-foaming cleaning agents for use in trade and industry, in particular for cleaning metal, glass and ceramic surfaces, generally contain foam-suppressing additives which are able to counteract undesirable foam development. This use of the foam-suppressing aids is mostly due to the fact that the detached from the substrates and in the cleaning baths accumulating impurities act as foaming agents. However, the cleaning agents themselves can also contain constituents which give rise to undesirable foaming under the given working conditions. An example of this are the widely used anionic surfactants.
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)-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 ein 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. There is described the use of end-capped polyethylene glycol ethers of the formula (I) R₁O- (CH₂CH₂O) -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.
Durch eine leichte Strukturvariation der genannten Fettalkoholpolyethylenglykolether ist es möglich, ein insbesondere verbessertes Arbeiten im niedrigeren Temperaturbereich, beispielsweise also im Bereich der Raumtemperatur oder bei nur schwach erhöhten Temperaturen zu erschließen. In der DE-OS 38 00 493 (D 8113) wird die Verwendung von Polyethylenglykolethern der zuvor angegebenen allgemeinen Formel (I) beschrieben, wobei jetzt aber in dieser Formel R₁ einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest mit 20 bis 28 C-Atomen, R₂ einen Alyklrest mit 4 bis 8 C-Atomen und n eine Zahl von 6 bis 20 bedeuten. Die entscheidende Abwandlung liegt hier in der Verwendung längerkettiger Reste R₁. Auch diese Endgruppenverschlossenen Polyglykolether zeichnen sich durch eine hohe Alkali- und Säurestabilität aus. Ihre schaumverhindernde Wirkung in alkalischen und neutralen Reinigungsflotten ist im angegebenen Sinne verstärkt, darüber hinaus erfüllen auch sie die gesetzlichen Anforderungen an die biologische Abbaubarkeit.A slight structural variation of the fatty alcohol polyethylene glycol ethers mentioned makes it possible to develop particularly improved work in the lower temperature range, for example in the region of room temperature or at only slightly elevated temperatures. DE-OS 38 00 493 (D 8113) describes the use of polyethylene glycol ethers of the general formula (I) given above, but now in this formula R 1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 carbon atoms, R₂ is an alkyl radical with 4 to 8 carbon atoms and n is a number from 6 to 20. The crucial modification here is the use of longer chain residues R 1. These end group-capped polyglycol ethers are also characterized by high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is specified in the Strengthens the senses, moreover they also meet the legal requirements for biodegradability.
Es ist bekannt, daß sich nichtionische Tenside auf Basis von Polyglykolether-Verbindungen nicht ohne weiteres in wäßrige, stark alkalische Formulierungen einarbeiten lassen. Sie bilden leicht eine von der wäßrigen getrennte Phase und bedürfen daher der Mitverwendung von Lösungsvermittlern. Bekannte wirkungsvolle Lösungsvermittler, insbesondere gerade auch für stark alkalische Reinigungsformulierungen sind Alkylmono- und/oder Oligoglucoside, die auch aus ökologischen Gründen heraus eine bevorzugte Stoffklasse im hier gegebenen Sachzusammenhang sein müssen.It is known that nonionic surfactants based on polyglycol ether compounds cannot easily be incorporated into aqueous, strongly alkaline formulations. They easily form a separate phase from the aqueous phase and therefore require the use of solubilizers. Known effective solubilizers, especially especially for strongly alkaline cleaning formulations, are alkyl mono- and / or oligoglucosides, which must also be a preferred class of substances in the given context for ecological reasons.
So beschreibt die EP-A2-0 202 638 ein flüssiges Reinigungskonzentrat für stark alkalische Reinigungsformulierungen bestehend aus Endgruppen-verschlossenen Fettalkoholglykolether-Verbindungen mit gemischten Oligoalkoxidresten zusammen mit einer Kombination von drei Lösungsvermittlern, die die homogene Formulierung in wäßrigen stark alkalischen Lösungen sicherstellen sollen. Der eine dieser mitverwendeten Lösungsvermittler sind Alkylmono- und/oder Alkylpolyglucoside mit 8 bis 12 C-Atomen im Alkylrest und 1 bis 6 Glukoseeinheiten. Auch in der US-PS 4,240,921 wird als alkalisches Waschmittelkonzentrat für die Flaschenwäsche ein wäßriges Konzentrat, enthaltend 10 bis 35 Gew.-% Alkalimetallhydroxid, 10 bis 50 Gew.-% einer Mischung eines Polyoxypropylen-polyoxyethylen-Kondensats, eines veretherten ethoxylierten Alkohols und eines Alkylglucosids beschrieben. Nachteilig ist insbesondere im Rahmen dieser zuletzt genannten Lehre, daß diese Zubereitungen bei der praktischen Anwendung insbesondere durch die Mitverwendung des Alkylglucosids zu stark schäumen. Zudem treten bei hohen Alkaligehalten Phasentrennungen auf.For example, EP-A2-0 202 638 describes a liquid cleaning concentrate for strongly alkaline cleaning formulations consisting of end group-capped fatty alcohol glycol ether compounds with mixed oligoalkoxide residues together with a combination of three solubilizers which are intended to ensure homogeneous formulation in strongly alkaline aqueous solutions. One of these solubilizers used is alkyl mono- and / or alkyl polyglucosides with 8 to 12 carbon atoms in the alkyl radical and 1 to 6 glucose units. Also in US Pat. No. 4,240,921 an alkaline detergent concentrate for washing bottles is an aqueous concentrate containing 10 to 35% by weight of alkali metal hydroxide, 10 to 50% by weight of a mixture of a polyoxypropylene-polyoxyethylene condensate, an etherified ethoxylated alcohol and one Alkylglucosids described. It is a disadvantage, particularly in the context of this last-mentioned teaching, that these preparations foam too much during practical use, in particular through the use of the alkylglucoside. In addition, phase separations occur at high alkali contents.
Die Lehre der vorliegenden Erfindung geht von der Aufgabe aus, durch eine Feinabstimmung und Optimierung in der Auswahl der eingesetzten Polyethylenglykolether-Verbindungen zu Stoffmischungen zu kommen, die sich durch besonders hochwertige Wirkungen bei ihrer Verwendung als Antischaummittel auszeichnen und dabei diese Wirkungsoptimierung sowohl bei vergleichsweise niederen Temperaturen - also beispielsweise im Bereich von etwa 20 °C - als auch bei den in der Praxis üblicherweise angewandten erhöhten Temperaturen im Bereich von etwa 60 bis 70 °C zugänglich werden lassen. Die Erfindung will weiterhin die Formulierung dieser Hilfsmittel in stark alkalischen, hochkonzentrierten wäßrigen Lösungen zu einphasigen Systemen ermöglichen. Dabei soll diese einphasige Formulierbarkeit über den in der Praxis wesentlichen Temperaturbereich, beispielsweise also von etwa 20 bis 70 °C gewährleistet sein.The teaching of the present invention is based on the task, by fine tuning and optimizing the selection of the polyethylene glycol ether compounds used, to obtain mixtures which are distinguished by particularly high-quality effects when used as anti-foaming agents, and this effect optimization both at comparatively low temperatures - So, for example, in the range of about 20 ° C - as well as at the elevated temperatures usually used in practice in the range of about 60 to 70 ° C. The invention further aims to enable the formulation of these auxiliaries in strongly alkaline, highly concentrated aqueous solutions to form single-phase systems. This single-phase formulability should be ensured over the temperature range that is essential in practice, for example from about 20 to 70 ° C.
Die Lehre der Erfindung baut auf der Erkenntnis auf, daß der gemeinsame Einsatz zweier strukturähnlicher, jedoch nicht strukturidentischer Polyethylenglykol-Verbindungen im Zusammenwirken mit den Alkylglucosiden dann zu der angestrebten Optimierung führt, wenn gleichzeitig die im nachfolgenden definierten Konstitutionsmerkmale für den Aufbau des jeweiligen Typs der Polyethylenglykolether-Verbindungen eingehalten werden.The teaching of the invention is based on the knowledge that the joint use of two structurally similar but not structurally identical polyethylene glycol compounds in cooperation with the alkyl glucosides leads to the desired optimization if at the same time the constitutional features defined below for the construction of the respective type of polyethylene glycol ether -Connections are observed.
Gegenstand der Erfindung ist dementsprechend die Verwendung eines gegebenenfalls Wasser in begrenzten Mengen enthaltenden Wirkstoffgemisches aus (Gew.-% jeweils bezogen auf Wirkstoffgemisch)
- 1. 5 bis 30 Gew.-% Alkylglucoside auf Basis von C₆₋₁₂-Fettalkoholen mit einem Glucosidierungsgrad von etwa 1 bis 2
- 2. 5 bis 70 Gew.-% Endgruppen-verschlossener Polyethylenglykolether-Verbindungen der allgemeinen Formel (I)
R₁O-(CH₂CH₂O)n-R₂ (I)
in der sich der Rest R₁O- von 2-verzweigten geradzahligen Alkanolen mit 16 bis 20 C-Atomen ableitet, der Rest R₂ einen Alkylrest mit 4 bis 8 C-Atomen und n eine Zahl von 5 bis 9 bedeuten - 3. 5 bis 70 Gew.-% nicht Endgruppen-verschlossener Polyethylenglykolether-Verbindungen der allgemeinen Formel (II)
R₅O-(CH₂CH₂O)z-H (II)
in der sich der Rest R₅O- von 2-verzweigten geradzahligen Alkanolen mit 12 bis 20 C-Atomen ableitet und z eine Zahl von 2 bis 5 ist,
sowie gewünschtenfalls - 4. 0 bis 70 Gew.-% Endgruppen-verschlossener Polyethylenglykolether-Verbindungen der allgemeinen Formel (III)
R₃O-(CH₂CH₂O)m-R₄ (III)
in der R₃ einen linearen Alkylrest mit 8 bis 18 C-Atomen oder einen verzweigten Alkylrest mit 8 bis 14 C-Atomen, R₄ einen Alkylrest mit 4 bis 10 C-Atomen und m eine Zahl von 5 bis 15 bedeuten, - 5. 0 bis 5 Gew.-% Alkali-Cumolsulfonat und/oder Alkali-Xylolsulfonat sowie
- 6. 0 bis 70 Gew.-% deionisiertes Wasser
- 1. 5 to 30 wt .-% alkyl glucosides based on C₆₋₁₂ fatty alcohols with a degree of glucosidation of about 1 to 2
- 2. 5 to 70% by weight of end-capped polyethylene glycol ether compounds of the general formula (I)
R₁O- (CH₂CH₂O) n -R₂ (I)
in which the radical R₁O is derived from 2-branched even alkanols with 16 to 20 C atoms, the radical R₂ is an alkyl radical with 4 to 8 C atoms and n is a number from 5 to 9 - 3. 5 to 70% by weight of non-end-capped polyethylene glycol ether compounds of the general formula (II)
R₅O- (CH₂CH₂O) z -H (II)
in which the radical R₅O- is derived from 2-branched even alkanols with 12 to 20 C atoms and z is a number from 2 to 5,
as well as if desired - 4. 0 to 70% by weight end-capped polyethylene glycol ether compounds of the general formula (III)
R₃O- (CH₂CH₂O) m -R₄ (III)
in which R₃ is a linear alkyl radical with 8 to 18 C atoms or a branched alkyl radical with 8 to 14 C atoms, R₄ is an alkyl radical with 4 to 10 C atoms and m is a number from 5 to 15, - 5. 0 to 5 wt .-% alkali cumene sulfonate and / or alkali xylene sulfonate and
- 6. 0 to 70% by weight of deionized water
Die Polyethylenglykolether-Verbindungen der Wirkstoffklasse (2) sind ausgewählte, Endgruppen-verschlossene Vertreter der hier betroffenen Stoffklasse. In einer bevorzugten Ausgestaltung der Erfindung leiten sich diese Verbindungen der allgemeinen Formel (I) bezüglich ihres Restes R₁O- von wenigstens einer der nachfolgenden Unterklassen ab:
- (2a) 2-Hexyldecanol-1
- (2b) 2-Octyldodecanol-1
- (2c) Gemische von (2a) und (2b), wobei Gemische mit 40 bis 70 Mol-% 2-Hexyldecanol-1 und 60 bis 30 Mol-% 2-Octyldodecanol-1 bevorzugt sein können
- (2d) Gemische aus
10 bis 100 Mol-% eines äquimolaren Isomerengemisches aus 2-Hexyldodecanol-1 und 2-Octyldecanol-1
0 bis 90 Mol-% 2-Hexyldecanol-1
0 bis 50 Mol-% 2-Octyldodecanol-1
wenigstens 45 Mol-% des Isomerengemisches aus 2-Hexyldodecanol-1 und 2-Octyldecanol-1,
0 bis 55 Mol-% 2-Hexyldecanol-1 und
nicht mehr als 30 Mol-% 2-Octyldodecanol-1.The polyethylene glycol ether compounds of the active substance class (2) are selected, end group-closed representatives of the substance class concerned here. In a preferred embodiment of the invention, these compounds are derived from the general formula (I) with respect to their rest R₁O- from at least one of the following subclasses:
- (2a) 2-Hexyldecanol-1
- (2b) 2-octyldodecanol-1
- (2c) Mixtures of (2a) and (2b), mixtures with 40 to 70 mol% of 2-hexyldecanol-1 and 60 to 30 mol% of 2-octyldodecanol-1 may be preferred
- (2d) mixtures of
10 to 100 mol% of an equimolar isomer mixture of 2-hexyldodecanol-1 and 2-octyldecanol-1
0 to 90 mol% of 2-hexyldecanol-1
0 to 50 mol% 2-octyldodecanol-1
at least 45 mol% of the isomer mixture of 2-hexyldodecanol-1 and 2-octyldecanol-1,
0 to 55 mol% of 2-hexyldecanol-1 and
not more than 30 mol% 2-octyldodecanol-1.
Die nicht Endgruppen-verschlossenen Polyethylenglykolether-Verbindungen der allgemeinen Formel (II), d. h. die Wirkstoffkomponenten zu (3) lassen bezüglich der Definition ihres Restes R₅O- eine etwas breitere Fassung zu. In Betracht kommen hier als Einsatzmaterial die 2-verzweigten geradzahligen Alkanole mit 12 bis 20 C-Atomen und damit insbesondere einer oder mehrere der folgenden Verbindungen:
- C12 2-Butyloctanol-1
- C14 Gemisch aus 2-Butyldecanol-1 und 2-Hexyloctanol-1
- C16 2-Hexyldecanol-1
- C18 Gemisch aus 2-Hexyldodecanol-1 und 2-Octyldecanol-1
- C20 2-Octyldodecanol-1
- C12 2-butyloctanol-1
- C14 mixture of 2-butyldecanol-1 and 2-hexyloctanol-1
- C16 2-hexyldecanol-1
- C18 mixture of 2-hexyldodecanol-1 and 2-octyldecanol-1
- C20 2-octyldodecanol-1
In einer besonderen Ausführungsform kann es zweckmäßig sein, als Wirkstoffkomponente zu (3) Verbindungen der allgemeinen Formel (II) einzusetzen, in denen sich der Rest R₅O- von Alkanolen bzw. Alkanolgemischen ableitet, die zur Bestimmung des Restes R₁O- aus der allgemeinen Formel (I) zuvor als Unterklassen (2a), (2b), (2c) und/oder (2d) definiert worden sind. Zusätzlich können hier - wie angegeben - aber auch solche Verbindungen der allgemeinen Formel (II) Verwendung finden, die bezüglich ihres Restes R₅O- von 2-Butyloctanol-1, 2-Butyldecanol-1 und/oder 2-Hexyloctanol-1 abgeleitet sind.In a particular embodiment, it may be expedient to use as active ingredient component to (3) compounds of the general formula (II) in which the R₅O- radical is derived from alkanols or alkanol mixtures which, for determining the R₁O- radical, are derived from the general formula ( I) have previously been defined as subclasses (2a), (2b), (2c) and / or (2d). In addition, as stated, compounds of the general formula (II) can also be used here which are derived from 2-butyloctanol-1, 2-butyldecanol-1 and / or 2-hexyloctanol-1 with respect to their radical R₅O-.
Die Wirkstoffe bzw. Wirkstoffgemische zu (2) und (3) der allgemeinen Formeln (I) und (II) liegen nach der Lehre der Erfindung zusammen mit den Alkylglucosiden vor. Gewünschtenfalls werden die Wirkstoffkomponenten zu den Ziffern (4) - d. h. die Endgruppen-verschlossenen Polyethylenglykolether-Verbindungen der allgemeinen Formel (III) -, Alkalisalze von Cumolsulfonat und/oder Xylolsulfonat sowie deionisiertes Wasser mitverwendet.According to the teaching of the invention, the active ingredients or active ingredient mixtures for (2) and (3) of the general formulas (I) and (II) are present together with the alkylglucosides. If desired, the active ingredient components to numbers (4) - d. H. the end group-capped polyethylene glycol ether compounds of the general formula (III) -, alkali metal salts of cumene sulfonate and / or xylene sulfonate and also deionized water.
Charakteristisch ist für die Erfindung die Verwendung der Wirkstoffkomponenten zu (2) und (3) gemeinsam mit den Alkylglucosiden. Zur Auswahl dieser erfindungsgemäßen Hilfsstoffe mit Tensidcharakter, gleichzeitig aber stark schaumdrückender Wirkung gilt das folgende:
Bei der Feinabstimmung der vielgestaltigen Anforderungen der Praxis an schaumdrückende Zusätze der hier betroffenen Art hat sich gezeigt, daß Stoffgemische der erfindungsgemäß definierten Art dann besonders wertvoll sind, wenn verzweigte Alkanole von der Art der Guerbet-Alkohole hier die Grundsubstanz bilden. 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. In einer besonderen Ausführungsform will dabei die Erfindung überwiegend oder bevorzugt ausschließlich geradkettige Fettalkohole zur Herstellung der 2-verzweigten Guerbet-Alkohole und letztlich dann zur Synthese der Verbindungen der allgemeinen Formel (I) einsetzen. Fettalkohole natürlichen Ursprungs haben bekanntlich wenigstens weitaus überwiegend geradzahlige Kettenlängen, so daß über ihre Dimerisierung der 2-verzweigte Guerbet-Alkohol mit 18 C-Atomen nicht als einheitliches Kondensationsprodukt nur eines ausgewählten Fettalkohols erhalten werden kann. Die hier notwendige Dimerisierung eines Gemisches der beiden Fettalkohole mit 8 und 10 C-Atomen führt zu dem Isomerengemisch des 18 C-Guerbet-Alkohols aus 2-Hexyldodecanol-1 und 2-Octyldecanol-1. Daneben entstehen die Kondensationsprodukte der beiden eingesetzten Alkohole mit sich selbst, d. h., das 2-Hexyldecanol-1 aus dem eingesetzten Octanol und das 2-Octyldodecanol-1 aus dem eingesetzten Decanol. Entsprechendes gilt für den 14 C-Guerbetalkohol bei seiner Herstellung aus geradzahligen Fettsäuren natürlichen Ursprungs sinngemäß.It is characteristic of the invention to use the active ingredient components for (2) and (3) together with the alkyl glucosides. The following applies to the selection of these auxiliaries according to the invention which have a surfactant character but at the same time have a strong foam-suppressing action:
When fine-tuning the diverse requirements in practice for foam-suppressing additives of the type concerned here, it has been found that substance mixtures of the type defined according to the invention are particularly valuable when branched alkanols of the Guerbet alcohol type form the basic substance here. 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, e.g. As potassium hydroxide or potassium alcoholate. The reaction takes place, for example, at temperatures from 200 to 300 ° C. and leads to branched Guerbet alcohols which have branching in the 2 position to the hydroxyl group. In a particular embodiment, the invention predominantly or preferably exclusively uses straight-chain fatty alcohols for the preparation of the 2-branched Guerbet alcohols and ultimately for the synthesis of the compounds of the general formula (I). It is known that fatty alcohols of natural origin have at least largely predominantly even chain lengths, so that their 2-branched Guerbet alcohol with 18 C atoms cannot be obtained as a uniform condensation product of only one selected fatty alcohol via their dimerization. The necessary dimerization of a mixture of the two fatty alcohols with 8 and 10 C atoms leads to the isomer mixture of the 18 C Guerbet alcohol from 2-hexyldodecanol-1 and 2-octyldecanol-1. In addition, the condensation products of the two alcohols used arise with themselves, ie the 2-hexyldecanol-1 from the octanol used and the 2-octyldodecanol-1 from the decanol used. The same applies analogously to 14 C Guerbet alcohol when it is produced from even-numbered fatty acids of natural origin.
Die Herstellung der Endgruppen-verschlossenen - aber auch der nicht mit Endgruppen-verschlossenen - Fettalkoholpolyglykolether der Formel (I) bzw. der Formel (II) 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 : 5 bis 1 : 9 bzw. 1 : 2 bis 1 : 5 um und verethert gewünschtenfalls anschließend die im erhaltenen Reaktionsprodukt vorhandenen Hydroxylgruppen. Die Umsetzung mit Ethylenoxid erfolgt dabei unter den bekannten Alkoxylierungsbedingungen, vorzugsweise in Gegenwart von geeigneten alkalischen Katalysatoren. Die Veretherung der freien Hydroxylgruppen wird bevorzugt unter den bekannten Bedingungen der Williamsonschen Ethersynthese mit geradkettigen oder verzweigten C₄- bis C₈-Alkylhalogeniden durchgeführt. Besondere Bedeutung kommt im Rahmen des erfindungsgemäßen Handelns dem n-Butylrest für den Rest R₂ aus der allgemeinen Forme (I) zu. Beispiele für eine solche abschließende Veretherung sind dementsprechend n-Butylhalogenide wie n-Butylchlorid. Die Erfindung ist allerdings hierauf nicht beschränkt. Weitere Beispiele sind Amylhalogenide, Hexylhalogenide und die höheren Alkylhalogenide des genannten Bereichs. Die Herstellung von Verbindungen der allgemeinen Formel (III) erfolgt sinngemäß.The end group-capped - but also those not capped with end groups - fatty alcohol polyglycol ethers of the formula (I) or of the formula (II) are prepared in accordance with the specifications of DE-OS 33 15 951. This is advantageously done the fatty alcohols of higher carbon number described above with ethylene oxide in a molar ratio of 1: 5 to 1: 9 or 1: 2 to 1: 5 μm and, if desired, then etherify 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 using straight-chain or branched C₄- to C₈-alkyl halides. The n-butyl radical for the radical R₂ from the general formula (I) is of particular importance in the course of the inventive action. Examples of such a final etherification are accordingly n-butyl halides such as n-butyl chloride. However, the invention is not limited to this. Further examples are amyl halides, hexyl halides and the higher alkyl halides in the range mentioned. Compounds of the general formula (III) are prepared analogously.
Dabei kann es zweckmäßig sein, Alkylhalogenid und Alkali im stöchiometrischen Überschuß, beispielsweise von 10 bis 50 %, über die zu verethernden Hydroxylgruppen einzusetzen. Die Reinigungsmittel, in denen die anteilsweise Endgruppen-verschlossenen Polyglykolethergemische 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 nicht ionogene oberflächenaktive Verbindungen vom Typ der 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, Alkylschwefelsauren, Alkylsulfonsäuren und Alkylbenzolsulfonsäuren in Betracht. An Gerüstsubstanzen und Komplexbildnern können die Reinigungsmittel vor allem Alkalimetallorthophosphate, -polymerphosphate, -silikate, -borate, -carbonate, -polyacrylate und -gluconate sowie Zitronensäure, Nitrilotriessigsäure, Ethylendiamintetraessigsäure, 1-Hydroxyalkan-1,1-diphosphonsäuren und Ethylendiamintetra-(methylenphosphonsäure), Phosphonoalkanpolycarbonsäuren, 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.It may be appropriate to use alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified. The cleaning agents in which the partially end-capped polyglycol ether mixtures of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and optionally also organic solvents. The surfactants used are non-ionic surface-active compounds of the polyglycol ether type which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consideration. At The cleaning agents can be builders and complexing agents, in particular 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 and ethylene Phosphonoalkane polycarboxylic acids, e.g. B. 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.
Entscheidend für die Lehre der Erfindung ist, daß die Herstellung von lagerstabilen, im Temperaturbereich von etwa 20 bis 60 °C bevorzugt klar flüssigen, wäßrig alkalischen Zubereitungen schaumdrückender Wirkstoffgemische möglich wird, die beispielsweise 5 bis 30 Gew.-% der Wirkstoffkonzentrate aus den Komponenten (1) bis (3) und gewünschtenfalls zusätzlich (4) bis (6) zusammen mit 70 bis 95 Gew.-% an konzentrierten wäßrigen Alkalihydroxidlösungen enthalten. Diese Alkalihydroxidlösungen können wäßrige Natrium- und/oder Kaliumhydroxidlösungen mit Gehalten des Alkalihydroxids von wenigstens 30 Gew.-%, insbesondere von wenigstens 40 Gew.-% sein. Geeignet ist beispielsweise wäßrige etwa 50%ige Natronlauge als Hauptanteil einer erfindungsgemäßen Formulierung, die bis etwa 70 °C lagerstabil als homogen klare wäßrige Lösung vorliegt.It is crucial for the teaching of the invention that it is possible to prepare storage-stable active ingredient mixtures which are foamable and preferably liquid in the temperature range from about 20 to 60 ° C. and which, for example, contain 5 to 30% by weight of the active ingredient concentrates from the components ( 1) to (3) and, if desired, additionally (4) to (6) together with 70 to 95% by weight of concentrated aqueous alkali metal hydroxide solutions. These alkali hydroxide solutions can be aqueous sodium and / or potassium hydroxide solutions with an alkali hydroxide content of at least 30% by weight, in particular at least 40% by weight. Suitable is, for example, aqueous approximately 50% sodium hydroxide solution as the main part of a formulation according to the invention, which is stable in storage up to approximately 70 ° C. as a homogeneously clear aqueous solution.
Die erfindungsgemäß zu verwendenden Polyglykolether-Gemische 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 polyglycol ether mixtures to be used according to the invention give effective effects even in low concentrations. Such detergents are preferred in such quantities added that their concentration in the ready-to-use solutions is approximately in the range of 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:
Die Prüfung der Entschäumungswirkung wird unter folgenden Bedingungen vorgenommen: In einem doppelwandigen 2-l-Meßzylinder werden 300 ml einer 1 gew.-%igen wäßrigen Natronlauge auf 20 °C bzw. 65 °C temperiert. Diese Lösung wird mit 0,1 ml des zu bestimmenden, entschäumend wirkenden Tensids versetzt. Mit Hilfe einer Schlauchpumpe wird die Flüssigkeit mit einer Umwälzgeschwindigkeit von 4 l/min. umgepumpt. Dabei wird die Prüfflotte ca. 5 mm über dem Boden des Meßzylinders mittels eines 55 cm langen Glasrohres (Innendurchmesser 8,5 mm, Außendurchmesser 11 mm), das mit der Pumpe über einen 1,6 m langen Silikonschlauch (Innendurchmesser 8 mm, Außendurchmesser 12 mm) verbunden ist, angesaugt und über ein zweites Glasrohr (Länge 20 cm), das an der 2000-ml-Marke des Meßzylinders 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:
The defoaming effect is tested under the following conditions: 300 ml of a 1% strength by weight aqueous sodium hydroxide solution are heated to 20 ° C. or 65 ° C. in a double-walled 2 liter measuring cylinder. 0.1 ml of the defoaming surfactant to be determined is added to this solution. With the help of a peristaltic pump, the liquid is circulated at a rate of 4 l / min. pumped around. The test liquor is approx. 5 mm above the bottom of the measuring cylinder using a 55 cm long glass tube (inner diameter 8.5 mm, outer diameter 11 mm), which is connected to the pump via a 1.6 m long silicone hose (inner diameter 8 mm, outer diameter 12 mm) is sucked in and returned in free fall via a second glass tube (length 20 cm) attached to the 2000 ml mark on the measuring cylinder.
Als Testschäumer dient eine 1 Gew.-%ige wäßrige Lösung des Triethanolaminsalzes von Tetrapropylenbenzolsulfonat. Diese wird in Abständen von jeweils einer Minute in Mengen von jeweils 1 ml der in Umwälzung befindlichen Flotte zudosiert. Das entstehende Gesamtvolumen von Schaum und Flüssigkeit wird bestimmt. Die schauminhibierende Wirkung des jeweils eingesetzten tensidischen Materials ist um so besser, je länger der Zeitraum ist, der zum Erreichen der 2000-ml-Markierung im Meßzylinder durch das Gesamtvolumen von Flüssig- und Schaumphase benötigt wird. In den nachfolgenden Beispielen sind die jeweiligen entsprechenden Zahlenwerte für diesen Zeitpunkt in Minuten bzw. in ml Testschäumer angegeben.A 1% by weight aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate is used as the test foam. This is metered in at intervals of one minute in amounts of 1 ml each of the liquor in circulation. The resulting total volume of foam and liquid is determined. The foam-inhibiting effect of the surfactant material used in each case is all the better the longer the period of time required to reach the 2000 ml mark in the measuring cylinder due to the total volume of the liquid and foam phases. In the following examples, the respective are corresponding Numerical values for this time are given in minutes or in ml of test foamers.
15 % Alkylglucosid
10 % R₁O-(CH₂CH₂O)₇-n-Butylether, abgeleitet von
R₁OH 28 % 2-Octyldodecanol-1
25 % 2-Hexyldodecanol-1
25 % 2-Octyldecanol-1
22 % 2-Hexyldecanol-1
10 % 2-Hexyldecanol-1, umgesetzt mit 2 Mol Ethylenoxid
2 % Cumolsulfonat
63 % Wasser (deionisiert)
Formulierung:
10 % Produkt A
90 % 50%ige NaOH-Lösung
ergeben ein lagerstabiles klar-flüssiges Produkt im Bereich 20 bis 60 °C.15% alkyl glucoside
10% R₁O- (CH₂CH₂O) ₇- n -butyl ether derived from
R₁OH 28% 2-octyldodecanol-1
25% 2-hexyldodecanol-1
25% 2-octyldecanol-1
22% 2-hexyldecanol-1
10% 2-hexyldecanol-1, reacted with 2 moles of ethylene oxide
2% cumene sulfonate
63% water (deionized)
Formulation:
10% product A
90% 50% NaOH solution
result in a storage-stable clear-liquid product in the range of 20 to 60 ° C.
15 % Alkylglucosid
20 % 2-Hexyldecanol-1, umgesetzt mit 2 Mol Ethylenoxid
2 % Cumolsulfonat
63 % Wasser (deionisiert)
Formulierung:
10 % Produkt B
90 % 50%ige NaOH-Lösung
ergeben bei 25 °C nach einigen Tagen ein trübes Produkt.15% alkyl glucoside
20% 2-hexyldecanol-1, reacted with 2 moles of ethylene oxide
2% cumene sulfonate
63% water (deionized)
Formulation:
10% product B
90% 50% NaOH solution
give a cloudy product at 25 ° C after a few days.
15 % Alkylglucosid
20 % R₁O-(CH₂CH₂O)₇-n-butylether gemäß "Produkt A"
2 % Cumolsulfonat
63 % Wasser (deionisiert)
Formulierung:
10 % Produkt C
90 % 50%ige NaOH-Lösung
ergeben bei 25 °C nach einigen Tagen ein trübes Produkt.15% alkyl glucoside
20% R₁O- (CH₂CH₂O) ₇-n-butyl ether according to "product A"
2% cumene sulfonate
63% water (deionized)
Formulation:
10% product C
90% 50% NaOH solution
give a cloudy product at 25 ° C after a few days.
15 % Alkylglucosid
20 % Kokosalkohol-10 EO-butylether
2 % Cumolsulfonat
63 % Wasser (deionisiert)
Formulierung:
10 % Produkt D
90 % 50%ige NaOH-Lösung
ergeben bei 20 °C ein klar-flüssiges Produkt.15% alkyl glucoside
20% coconut alcohol-10 EO-butyl ether
2% cumene sulfonate
63% water (deionized)
Formulation:
10% product D
90% 50% NaOH solution
result in a clear, liquid product at 20 ° C.
jeweils mit 0,5 ml der Produkte A, B, C und D (entspricht 0,1 ml des in diesen Produkten enthaltenen Antischaummittels).
Nur Produkt A ist formulierbar und weist eine gute Antischaumwirkung bei 20 und 65 °C auf.Only product A can be formulated and has a good anti-foam effect at 20 and 65 ° C.
Claims (5)
- The use of an active-substance mixture - optionally containing water in limited quantities - of (% by weight, based on the mixture as a whole)1. 5 to 30% by weight alkyl glucosides based on C₆₋₁₂ fatty alcohols having a degree of glucosidation of about 1 to 22. 5 to 70% by weight end-capped polyethylene glycol ether compounds corresponding to general formula (I)
R₁O-(CH₂CH₂O)n-R₂ (I)
in which the function R₁O- is derived from 2-branched, even-numbered alkanols containing 16 to 20 carbon atoms, R₂ is an alkyl radical containing 4 to 8 carbon atoms and n is a number of 5 to 9,3. 5 to 70% by weight non-end-capped polyethylene glycol ether compounds corresponding to general formula (II)
R₅O-(CH₂CH₂O)z-H (II)
in which the function R₅O- is derived from 2-branched even-numbered alkanols containing 12 to 20 carbon atoms and z is a number of 2 to 5,
and, if desired,4. 0 to 70% by weight end-capped polyethylene glycol ether compounds corresponding to general formula (III)
R₃O-(CH₂CH₂O)m-R₄ (III)
in which R₃ is a linear alkyl radical containing 8 to 18 carbon atoms or a branched alkyl radical containing 8 to 14 carbon atoms, R₄ is an alkyl radical containing 4 to 10 carbon atoms and m is a number of 5 to 15,5. 0 to 5% by weight alkali metal cumenesulfonate and/or alkali metal xylenesulfonate and6. 0 to 70% by weight deionized wateras a foam-inhibiting active-substance concentrate capable of formulation into stable aqueous alkali solutions for low-foaming cleaning products. - The use claimed in claim 1, characterized in that polyglycol ether compounds corresponding to general formula (I), in which the function R₁O- is derived from the following alcohol mixtures (a) or (b):a) 10 to 100 mol-% of an equimolar isomer mixture of 2-hexyl-1-dodecanol and 2-octyl-1-decanolor
0 to 90 mol-% 2-hexyl-1-decanol
0 to 50 mol-% 2-octyl-1-dodecanolb) 40 to 70 mol-% 2-hexyl-1-decanoland n is a number of 5 to 9,
60 to 30 mol-% 2-octyl-1-dodecanol
are used. - The use claimed in claims 1 and 2, characterized in that polyethylene glycol ether mixtures corresponding to general formula (I), of which the functions R₁O- are derived from alcohol mixtures having the following composition: at least 45 mol-% of the isomer mixture of 2-hexyl-1-dodecanol and 2-octyl-1-decanol, 0 to 55 mol-% 2-hexyl-1-decanol and no more than 30 mol-% 2-octyl dodecanol, are used.
- The use claimed in claims 1 to 3, characterized in that polyethylene glycol ether compounds corresponding to general formula (II), in which the function R₅O- is derived from at least one of the following alkanols: 2-butyl-1-octanol, 2-butyl-1-decanol, 2-hexyl-1-octanol, 2-hexyl-1-decanol, 2-hexyl-1-dodecanol, 2-octyl-1-decanol and/or 2-octyl-1-dodecanol, are used.
- Storable, aqueous-alkaline preparations of foaminhibiting -active-substance mixtures preferably in the form of clear liquids at temperatures of about 20 to 60°C containing
5 to 30% by weight of the active-substance concentrates claimed in claims 1 to 4 and
70 to 95% by weight concentrated aqueous alkali metal hydroxide solution preferably having MeOH contents (Me = sodium and/or potassium) of at least 30% by weight and, more preferably, at least 40% by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3928602 | 1989-08-30 | ||
| DE3928602A DE3928602A1 (en) | 1989-08-30 | 1989-08-30 | ALKALISTABLE AND STRONG ALKALINE-MOLDABLE ANTI-FOAM AGENTS FOR COMMERCIAL CLEANING, ESPECIALLY FOR BOTTLE AND CIP CLEANING |
| PCT/EP1990/001382 WO1991003538A1 (en) | 1989-08-30 | 1990-08-21 | Anti-foaming agents stable in alkali |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0489777A1 EP0489777A1 (en) | 1992-06-17 |
| EP0489777B1 true EP0489777B1 (en) | 1994-04-27 |
Family
ID=6388138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90912683A Expired - Lifetime EP0489777B1 (en) | 1989-08-30 | 1990-08-21 | Anti-foaming agents stable in alkali |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5205959A (en) |
| EP (1) | EP0489777B1 (en) |
| JP (1) | JPH05500074A (en) |
| CA (1) | CA2065334A1 (en) |
| DE (2) | DE3928602A1 (en) |
| ES (1) | ES2052268T3 (en) |
| WO (1) | WO1991003538A1 (en) |
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| DE3928604A1 (en) * | 1989-08-30 | 1991-03-07 | Henkel Kgaa | USE OF SELECTED MIXTURES OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM DETERGENTS |
| DE4009533A1 (en) * | 1990-03-24 | 1991-09-26 | Henkel Kgaa | LOW-EFFICIENT NON-ionic surfactant mix |
| US5538669A (en) * | 1990-11-09 | 1996-07-23 | Henkel Kommanditgesellschaft Auf Aktien | Stabilized surfactant paste |
| DE4116406A1 (en) * | 1991-05-18 | 1992-11-19 | Henkel Kgaa | USE OF DIALKYL ETHERS AS FOAM REGULATORS |
| DE4210365C2 (en) * | 1992-03-30 | 1995-06-08 | Henkel Kgaa | Use of cleaning agents for hard surfaces |
| GB9225075D0 (en) * | 1992-12-01 | 1993-01-20 | Ici Plc | Low foam polyglycoside formulations |
| DE4320119A1 (en) * | 1993-06-18 | 1994-12-22 | Henkel Kgaa | Liquid crystalline aqueous surfactant preparation |
| DE4323252C2 (en) * | 1993-07-12 | 1995-09-14 | Henkel Kgaa | Rinse aid for machine cleaning hard surfaces |
| DE59405262D1 (en) * | 1993-09-02 | 1998-03-19 | Henkel Kgaa | USE OF AQUEOUS DETERGENT MIXTURES |
| DE4342214C1 (en) * | 1993-12-10 | 1995-05-18 | Henkel Kgaa | Nonionic detergent mixtures |
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| US5576284A (en) * | 1994-09-26 | 1996-11-19 | Henkel Kommanditgesellschaft Auf Aktien | Disinfecting cleanser for hard surfaces |
| EP0709450A1 (en) * | 1994-10-24 | 1996-05-01 | The Procter & Gamble Company | Low sudsing liquid detergent compositions |
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| GB9606913D0 (en) | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
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| FR2754739B1 (en) * | 1996-10-22 | 1998-12-18 | Seppic Sa | ANTI-FOAM COMPOSITIONS AND INTERMEDIATE ANHYDROUS COMPOSITIONS |
| DE19738866A1 (en) | 1997-09-05 | 1999-03-11 | Henkel Kgaa | Low-foaming surfactant mixtures with hydroxy mixed ethers |
| SE510989C2 (en) * | 1997-10-29 | 1999-07-19 | Akzo Nobel Nv | Highly alkaline compositions containing a hexyl glycoside as a hydrotrope |
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| EP2152842B1 (en) * | 2007-05-11 | 2017-10-11 | Ecolab Inc. | Cleaning of polycarbonate |
| FR2968003B1 (en) * | 2010-11-25 | 2013-06-07 | Seppic Sa | NOVEL HYDROTROPE AGENT, ITS USE FOR SOLUBILIZING NO-IONIC SURFACTANTS, COMPOSITIONS COMPRISING SAME |
| FR2975703B1 (en) * | 2011-05-27 | 2013-07-05 | Seppic Sa | NOVEL USE OF HEPTYLPOLYGLYCOSIDES FOR SOLUBILIZING NONIONIC SURFACTANTS IN AQUEOUS ACID CLEANING COMPOSITIONS, AND AQUEOUS ACID CLEANING COMPOSITIONS COMPRISING SAME. |
| JP2011252160A (en) * | 2011-08-01 | 2011-12-15 | Adeka Corp | Cip cleaning method |
| EP2968092B1 (en) * | 2013-03-15 | 2020-05-27 | Croda, Inc. | Alkoxylated fatty alcohol alkyl ethers and products containing same |
| AU2013408755B2 (en) * | 2013-12-29 | 2017-05-25 | Halliburton Energy Services, Inc. | Lubricant for high pH water based mud system |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3018135A1 (en) * | 1980-05-12 | 1981-11-19 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING POLYGLYKOLETHERMAL FORMALS AND NEW POLYGLYKOLETHERMAL FORMALS |
| 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 |
| DE3518672A1 (en) * | 1985-05-24 | 1986-11-27 | Basf Ag, 6700 Ludwigshafen | LIQUID CLEANING CONCENTRATE FOR STRONG ALKALINE CLEANING FORMULAS |
| DE3531212A1 (en) * | 1985-08-31 | 1987-03-05 | Henkel Kgaa | ALKYLENE OXIDE BLOCK POLYMERS TO BE USED AS A DEFOAMER |
| DE3773781D1 (en) * | 1986-07-24 | 1991-11-21 | Henkel Kgaa | LOW-FOAM AND / OR FOAM-ABSORBING SURFACTANT MIXTURES AND THEIR USE. |
| SE462599B (en) * | 1987-04-06 | 1990-07-23 | Berol Kemi Ab | PRE-PACKING THAT PREVENTS FOAM PREPARATION, PREPARING SUCH PRE-PACKAGING AND ANTI-DUMPING AGENTS |
| DE3723323C2 (en) * | 1987-07-15 | 1998-03-12 | Henkel Kgaa | Hydroxy mixed ethers, processes for their preparation and their use |
| DE3727378A1 (en) * | 1987-08-17 | 1989-03-02 | Henkel Kgaa | FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS |
| DE3800493A1 (en) * | 1988-01-11 | 1989-07-20 | Henkel Kgaa | USE OF POLYGLYKOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANING AGENTS, IN PARTICULAR ALSO SUITABLE FOR COLD CLEANING |
| DE3800490A1 (en) * | 1988-01-11 | 1989-07-20 | Henkel Kgaa | USE OF SELECTED END-GROUP-CONTAINED FAT ALCOHOL ETHHOXYLATES FOR FOAM ARMS, COLD-FRYABLE CLEANING AGENTS |
| JPH01213564A (en) * | 1988-02-23 | 1989-08-28 | Japan Gore Tex Inc | Humidity-sensitive element and its manufacture |
| DE3818014A1 (en) * | 1988-05-27 | 1989-11-30 | Henkel Kgaa | FOAM-PRESSING ALKYL POLYGLYCOLETHER FOR CLEANING AGENTS (II) |
| DE3818062A1 (en) * | 1988-05-27 | 1989-12-07 | Henkel Kgaa | FOAMING ALKYL POLYGLYCOLETHER FOR CLEANING AGENT (I) |
-
1989
- 1989-08-30 DE DE3928602A patent/DE3928602A1/en not_active Withdrawn
-
1990
- 1990-08-21 EP EP90912683A patent/EP0489777B1/en not_active Expired - Lifetime
- 1990-08-21 JP JP2511738A patent/JPH05500074A/en active Pending
- 1990-08-21 US US07/835,922 patent/US5205959A/en not_active Expired - Fee Related
- 1990-08-21 CA CA002065334A patent/CA2065334A1/en not_active Abandoned
- 1990-08-21 ES ES90912683T patent/ES2052268T3/en not_active Expired - Lifetime
- 1990-08-21 WO PCT/EP1990/001382 patent/WO1991003538A1/en active IP Right Grant
- 1990-08-21 DE DE59005551T patent/DE59005551D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5205959A (en) | 1993-04-27 |
| DE59005551D1 (en) | 1994-06-01 |
| JPH05500074A (en) | 1993-01-14 |
| ES2052268T3 (en) | 1994-07-01 |
| WO1991003538A1 (en) | 1991-03-21 |
| EP0489777A1 (en) | 1992-06-17 |
| DE3928602A1 (en) | 1991-03-07 |
| CA2065334A1 (en) | 1991-03-01 |
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