EP3508563A1 - Use of o/w emulsions for chain lubrication - Google Patents
Use of o/w emulsions for chain lubrication Download PDFInfo
- Publication number
- EP3508563A1 EP3508563A1 EP19152794.4A EP19152794A EP3508563A1 EP 3508563 A1 EP3508563 A1 EP 3508563A1 EP 19152794 A EP19152794 A EP 19152794A EP 3508563 A1 EP3508563 A1 EP 3508563A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oder
- bis
- emulsion
- und
- mit
- 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.)
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- 238000005461 lubrication Methods 0.000 title abstract description 13
- 239000007764 o/w emulsion Substances 0.000 title description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 99
- 239000000314 lubricant Substances 0.000 claims abstract description 50
- 239000012141 concentrate Substances 0.000 claims abstract description 27
- 239000004164 Wax ester Substances 0.000 claims abstract description 18
- 235000019386 wax ester Nutrition 0.000 claims abstract description 18
- 235000013305 food Nutrition 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 150000002191 fatty alcohols Chemical class 0.000 claims description 24
- 150000003626 triacylglycerols Chemical class 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000005456 glyceride group Chemical group 0.000 claims description 17
- 229920000151 polyglycol Polymers 0.000 claims description 17
- 239000010695 polyglycol Substances 0.000 claims description 17
- 230000001050 lubricating effect Effects 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 11
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 230000000295 complement effect Effects 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- -1 fatty acid salts Chemical class 0.000 description 109
- 239000000203 mixture Substances 0.000 description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 27
- 150000001412 amines Chemical class 0.000 description 24
- 229920006395 saturated elastomer Polymers 0.000 description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 23
- 239000012071 phase Substances 0.000 description 20
- 229910052736 halogen Inorganic materials 0.000 description 18
- 150000002367 halogens Chemical class 0.000 description 18
- 125000001424 substituent group Chemical group 0.000 description 18
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- 238000000034 method Methods 0.000 description 16
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- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
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- 239000004094 surface-active agent Substances 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
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- 229940067606 lecithin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
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- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
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- 125000005609 naphthenate group Chemical group 0.000 description 1
- WRPMUZXHQKAAIC-CZIZESTLSA-N octadecyl (e)-octadec-9-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCC\C=C\CCCCCCCC WRPMUZXHQKAAIC-CZIZESTLSA-N 0.000 description 1
- ZFCUBQOYWAZKNO-ZPHPHTNESA-N octadecyl (z)-docos-13-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCC\C=C/CCCCCCCC ZFCUBQOYWAZKNO-ZPHPHTNESA-N 0.000 description 1
- GAQPWOABOQGPKA-UHFFFAOYSA-N octadecyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCCCCCCCC GAQPWOABOQGPKA-UHFFFAOYSA-N 0.000 description 1
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- BARWIPMJPCRCTP-UHFFFAOYSA-N oleic acid oleyl ester Natural products CCCCCCCCC=CCCCCCCCCOC(=O)CCCCCCCC=CCCCCCCCC BARWIPMJPCRCTP-UHFFFAOYSA-N 0.000 description 1
- 229940120511 oleyl erucate Drugs 0.000 description 1
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([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
- JYTMDBGMUIAIQH-ZPHPHTNESA-N palmityl oleate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC JYTMDBGMUIAIQH-ZPHPHTNESA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
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- 235000019149 tocopherols Nutrition 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
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- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
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- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/34—Esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/18—Ethers, e.g. epoxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/40—Esters containing free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
- C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M129/30—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
- C10M173/025—Lubricating compositions containing more than 10% water not containing mineral or fatty oils for lubricating conveyor belts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
- C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
- C10M2229/0465—Siloxanes with specific structure containing silicon-oxygen-carbon bonds used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/38—Conveyors or chain belts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
- C10N2050/013—Water-in-oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
- C10N2060/06—Chemical after-treatment of the constituents of the lubricating composition by epoxydes or oxyalkylation reactions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- the present invention relates to the use of an O / W emulsion, in particular a PIT emulsion, for the lubrication of conveyor belt systems in food processing plants and a lubricant concentrate based on wax esters.
- the containers to be filled in the bottling plants are transported by transporters of various designs and materials, for example via plate conveyor belts or chain-like arrangements, which will generally be referred to below as transport chains.
- the transporters make the connection between the different optional treatment stages of the filling process such.
- the containers may be various forms, in particular glass and plastic bottles, cans, jars, barrels, beverage containers (CEC), paper and cardboard containers.
- CEC beverage containers
- the transport chains In order to ensure trouble-free operation, the transport chains must be lubricated in a suitable manner, so that excessive friction with the containers is avoided.
- dilute aqueous solutions containing suitable friction-reducing agents are used for lubrication. With the aqueous solutions, the transport chains are brought into contact, for example by immersion or by spraying, which then speaks of immersion lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
- the chain lubricants hitherto used as lubricants are usually based on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts.
- Lubricants based on N-alkylated fatty amine derivatives which contain at least one secondary and / or tertiary amine.
- the WO 94/03562 describes a lubricant concentrate based on fatty amines and optionally conventional diluents or auxiliaries or additives, characterized in that it contains at least one polyamine derivative of a fatty amine and / or a salt of such an amine, wherein the proportion of said polyamine derivatives of fatty amines in the overall formulation to 100 wt .-% is.
- the registration DE 199 42 535.3 provides lubricants based on polyhydroxy compounds, which are hydrophilic due to their molecular structure and at the same time improve the lubricating performance over amines commonly used as lubricants.
- polyhydroxy compounds which are selected from alkanediols or alkanetriols, very particularly preferably glycerol, or their polymers and their esters and ethers.
- chain lubricants adhere very well to the chains, as is the case with the very well-wetting fluorosurfactants, for example, forms the transport chains a firmly adhering film that is not easy to remove by rinsing with water.
- the subject of the present invention is the use of an O / W emulsion in concentrated form or after dilution with water for lubricating conveyor belts in food processing plants.
- phase inversion oil-in-water emulsions, henceforth called O / W emulsions, prepared and stabilized with nonionic emulsifiers undergo phase inversion upon heating.
- phase inversion it is to be understood that at higher temperatures the outer, aqueous phase becomes the inner phase.
- This process is usually reversible, which means that the original emulsion type re-forms on cooling.
- location of the phase inversion temperature depends on many factors, for example the type and the phase volume of the oil component, the hydrophilicity and the structure of the emulsifier or the composition of the emulsifier system, compare for example! K. Shinoda and H.
- the German patent application DE-OS-38 19 193 describes a process for the preparation of low-viscosity O / W emulsions of polar oil components, which is based on the method of phase inversion temperature (PIT method).
- phase inversion temperatures below 100 ° C. are achieved by the presence of further coemulsifiers in addition to nonionic emulsifiers.
- O / W emulsions based on polar oil bodies and non-ionic emulsifiers are then particularly finely divided and long-term stable when a mixture of polar oil, nonionic emulsifier and a special interface moderator to a temperature within or above the phase inversion temperature range heated - or the emulsion prepares at this temperature - and then the emulsion is cooled to a temperature below the Phaseninversion-Tempertur Schemees and optionally further diluted with water.
- This method has the advantage that particularly finely divided emulsions are obtained which have excellent storage stability. Compared to the hitherto known state of the art, for example the DE-OS-38 19 193 , In addition, the phase inversion temperature is lowered, which is particularly favorable in practice because of the associated energy savings.
- the oil-in-water emulsions prepared by the PIT method find use, e.g. as a skin and body care product, as a cooling lubricant or as a textile and fiber auxiliary. They are particularly preferred in processes for the preparation of emulsion-like preparations for skin and hair treatment.
- German patent DE 197 03 087 C2 from which the use of appropriate PIT emulsions for the production of cosmetic refatting agents is known.
- the O / W emulsion contains at least one wax ester.
- Wax esters are esters of long-chain carboxylic acids with long-chain alcohols, which preferably follow the formula (1), R 1 CO-OR 2 (1) in which R 1 CO is a saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and R 2 is an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms.
- Triglycerides are substances of the formula (2),
- R 4 CO and R 5 CO independently represent linear or branched, saturated and / or unsaturated, optionally hydroxy- and / or epoxy-substituted acyl radicals having 6 to 22, preferably 12 to 18 carbon atoms and the sum (m + n + p) is 0 or numbers from 1 to 100, preferably 20 to 80.
- the triglycerides may be of natural origin or synthetically produced.
- hydroxy- and / or epoxy-functionalized substances such as, for example, castor oil or hydrogenated castor oil, epoxidized castor oil, ring opening products of epoxidized castor oils of different epoxide numbers with water and addition products of on average from 1 to 100, preferably from 20 to 80 and in particular from 40 to 60 mol these triglycerides.
- Partial glycerides are monoglycerides, diglycerides and their technical mixtures, which may still contain small amounts of triglycerides due to their production.
- the partial glycerides preferably follow the formula (3), in the R 6 CO for a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms, R 7 and R 8 are independently R 6 CO or OH and the sum (m + n + p ) is 0 or numbers from 1 to 100, preferably 5 to 25, with the proviso that at least one of the two radicals R 7 and R 8 is OH.
- Typical examples are mono- and / or diglycerides based on caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, Petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
- the fatty alcohol polyglycol ethers according to the invention correspond to the formula (4) , R 9 O (CH 2 CH 2 O) q H (4) in which R 9 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q is a number from 1 to 50.
- Typical examples are adducts of an average of 1 to 50, preferably 5 to 25, of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol , Elaeostearylalkohol, arachyl alcohol, Gadoleylalkohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures.
- the surfactants may have both a conventional broad and a narrow homolog distribution. Particularly preferred are addition products of on average 10 or 20 moles of ethylene oxide to cetearyl alcohol, stearyl alcohol and / or behenyl alcohol.
- the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
- C 8/18 alkyl mono- and oligoglycosides their preparation and their use as surfactants are for example US 3,839,318 . US 3,707,535 . US 3,547,828 . DE-OS 19 43 689 . DE-OS 20 36 472 and DE-A1 30 01 064 such as EP-A 0 077 167 known. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms.
- glycoside both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol, as well as oligomeric glycosides having a degree of oligomerization preferably up to about 8 are suitable.
- the degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.
- zwitterionic surfactants can be used as emulsifiers.
- Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
- Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylam-moniumglycinat, N-acylamino-propyl-N, N-dimethylammoniumglycinate, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
- betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylam-moniumglycinat, N-acylamino-propyl-N, N-dimethylammoniumglycinate, for example cocoacy
- fatty acid amide derivative known by the CTFA name cocamidopropylbetaine.
- emulsifiers are ampholytic surfactants.
- Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C 8/18 alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts.
- ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine.
- quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
- substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.
- the consistency factors used are first and foremost fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.
- suitable thickening agents are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, Alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, also higher molecular weight polyethylene glycol mono- and di-esters of fatty acids, polyacrylates (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted homolog distribution or alkyloligoglucosides and electrolytes such as common salt and ammonium chloride.
- polysaccharides in particular xanthan gum, guar guar, agar agar, Alginates and tyloses
- suitable cationic polymers are, for example, selected from cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF), Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimony hydroxy-propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amidomethicones, copolymers of adipic acid and Dimethylaminohydroxypropyldieth
- At least one alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds is selected in combination with at least one further component nitrogen-containing, aliphatic, organic compounds having less than 10 C atoms in the molecule, preferably less than 7 C atoms in the molecule, which particularly preferably contains an additional OH group, and / or d) an organic carboxylic acid having 1 to 10 carbon atoms in the molecule, preferably acetic acid and / or caproic acid.
- the proportion of said alcoholic component, based on the total Q / W emulsion to be used according to the invention is greater than 20% by weight, particularly preferably greater than 50% by weight, but not greater than 61.8 Wt .-% is.
- said alcoholic component to be used in the O / W emulsion to be used in the present invention is substantially glycerol.
- the nitrogen-containing compound (d) is present in the O / W emulsion to be used according to the invention, its proportion, based on the total concentrate, is 0.1 to 20% by weight.
- organic carboxylic acid (s) is present, their proportion, based on the total concentrate, 0.1 to 20 wt .-%.
- the proportion of the aqueous phase in the O / W emulsion to be used according to the invention is greater than 95% by weight, based on the total O / W emulsion.
- aqueous phase in the sense of the available invention are at least 10 Gew. -% water together with all contained therein Understand components with the proviso that together they represent a single phase, without phase boundaries.
- the O / W emulsion to be used according to the invention additionally comprises at least one antimicrobial component selected from the groups of the alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen , Nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate , Iodine, iodophores, peroxides, peracids, wherein the components mentioned are different from the previously mentioned components contained in the O / W emulsion to be used according to the invention
- the O / W emulsion to be used according to the invention is produced immediately prior to application to the belts of said conveyor belt system, it being particularly preferred if the preparation of said O / W emulsion in particular for the production of O / W emulsions suitable mixing nozzles takes place.
- the invention to be used O / W emulsion or its dilute solution for the transport of plastic, cardboard, metal or Glass containers used in the case of plastic containers these more preferably at least one polymer selected from the groups of polyethylene terephthalates (PET), polyethylene naphthenates (PEN), polycarbonates (PC), PVC and very particularly preferably PET beverage bottles are ,
- O / W emulsion when using the O / W emulsion to be used according to the invention, it is preferred that separately additional antimicrobial agents, in particular organic peracids, chlorine dioxide or ozone, be used in the application.
- additional antimicrobial agents in particular organic peracids, chlorine dioxide or ozone
- the O / W emulsion In the application of the O / W emulsion to be used according to the invention, it is further preferred to apply the O / W emulsion directly without prior dilution via an application device to the belts of the transport system.
- the O / W emulsion in the application of the O / W emulsion to be used according to the invention, it is preferred to dilute the O / W emulsion in the transport system with water, more preferably by a dilution factor of between 20,000 and 100, before it has an application device the belts of the transport system is applied.
- the application device in direct contact with the surfaces to be lubricated during application.
- the application for example via brush, sponge, cloth, wiper, which are in direct contact with the chain occurs.
- Another object of the present invention is a present as O / W emulsion lubricant concentrate containing a wax ester, for the lubrication of conveyor belts in food processing plants.
- Chain lubricant concentrates were formulated as O / W emulsion in different compositions and examined for their properties.
- the viscosity of formulations E1 and E2 was determined by the Brookfield method in an RVF viscometer (spindle 1, 10 revolutions per minute (rpm)) once immediately after preparation (20 ° C.) and once again after a storage time of 4 weeks measured at 45 ° C.
- the stability of the formulations was determined optically after storage (4 °, 45 ° C.). Where “+” means stable and "-" means phase separation.
- Lubricating tests were carried out with the formulations E1 and E3, as well as E4.
- the product was diluted with water of different quality in order to determine a dependence of the lubricating behavior on the water quality.
- PET bottles were tested in lubricant tests on test transporters. The experiments were carried out in the manner described in the prior art.
- the formulation E1 has excellent lubricating properties, especially with saline, hard water.
- the formulations E3 and E4 show very good values even in demineralized water.
- the present invention also enriches the selection of formulation resources for the application engineer.
- the lubricant concentrates combined with amine-containing chain lubricant agents are generally sufficiently effective antimicrobial to prevent in practice germ growth or even kill germs. If these combination active ingredients are lacking or if their concentration is not high enough, further antimicrobial active ingredients can of course be added if required.
- the TNO method was used.
- the formulation E1 was used without dilution and as an application solution with 1%.
- PET bottles are filled with water and conditioned with carbon dioxide in such a way that there is a pressure of about 7 bar inside the bottles. Thereafter, the bottoms of the bottles are immersed in the formulation of the comparative example or the example to be used according to the invention and placed in a petri dish over a period of 24 hours. After the 24 hours, the bottles are opened, emptied and the floor cups rinsed with water.
- the floor cups In the case of visual evaluation of the floor cups, it can be stated that in the experiment with the example to be used according to the invention, it can be established that only a few stress cracks with a shallow depth, classification A, are present in the floor area. The classification is based on the reference pictures, which are given in chapter IV-22 of the book 'CODE OF PRACTICE - Guidelines for an Industrial Code of Practice for Refillable PET Bottles', Edition 1, 1993-1994 , are included.
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Abstract
Die Erfindung betrifft die Verwendung einer O/W-Emulsion, insbesondere einer PIT-Emulsion, zur Schmierung von Transportbandanlagen in Lebensmittelbetrieben sowie ein Schmiermittelkonzentrat auf Basis einer O/W-Emulsion, insbesondere einer PIT-Emulsion, von Wachsester.The invention relates to the use of an O / W emulsion, in particular a PIT emulsion, for the lubrication of conveyor belts in food processing plants and a lubricant concentrate based on an O / W emulsion, in particular a PIT emulsion of wax esters.
Description
Die vorliegende Erfindung betrifft die Verwendung einer O/W-Emulsion, insbesondere einer PIT-Emulsion, zur Schmierung von Transportbandanlagen in Lebensmittelbetrieben sowie ein Schmiermittelkonzentrat auf Basis von Wachsester.The present invention relates to the use of an O / W emulsion, in particular a PIT emulsion, for the lubrication of conveyor belt systems in food processing plants and a lubricant concentrate based on wax esters.
In der Lebensmittelindustrie, insbesondere in Getränkebetrieben werden die in den Abfüllanlagen zu befüllenden Behälter über Transporteure verschiedenster Ausgestaltung und Materialien, beispielsweise über Plattentransportbänder oder kettenartige Anordnungen, die im folgenden allgemein als Transportketten bezeichnet werden sollen, transportiert. Die Transporteure stellen die Verbindung her zwischen den verschiedenen optionalen Behandlungsstufen des Abfüllprozesses wie z. B. Auspacker, Flaschenreinigungsmaschine, Füller, Verschließer, Etikettierer, Einpacker u.a.. Bei den Behältern kann es sich um verschiedenste Formen handeln, insbesondere Glas- und Kunststoffflaschen, Dosen, Gläser, Fässer, Getränkecontainer (KEG), Papier- und Pappbehälter. Um den störungsfreien Betrieb zu gewährleisten, müssen die Transportketten in geeigneter Weise geschmiert werden, so dass eine zu starke Reibung zu den Behältern vermieden wird. Üblicherweise werden zur Schmierung verdünnte wässrige Lösungen verwendet, die geeignete reibungsvermindernde Wirkstoffe enthalten. Mit den wässrigen Lösungen werden die Transportketten beispielsweise durch Eintauchen oder durch Besprühen in Kontakt gebracht, wobei man dann von Tauchschmieranlagen oder automatischen Bandschmiersystemen oder zentralen Kettenschmiersystemen spricht.In the food industry, especially in beverage companies, the containers to be filled in the bottling plants are transported by transporters of various designs and materials, for example via plate conveyor belts or chain-like arrangements, which will generally be referred to below as transport chains. The transporters make the connection between the different optional treatment stages of the filling process such. The containers may be various forms, in particular glass and plastic bottles, cans, jars, barrels, beverage containers (CEC), paper and cardboard containers. In order to ensure trouble-free operation, the transport chains must be lubricated in a suitable manner, so that excessive friction with the containers is avoided. Usually, dilute aqueous solutions containing suitable friction-reducing agents are used for lubrication. With the aqueous solutions, the transport chains are brought into contact, for example by immersion or by spraying, which then speaks of immersion lubrication systems or automatic belt lubrication systems or central chain lubrication systems.
Die bisher als Schmiermittel eingesetzten Kettengleitmittel basieren meist auf Fettsäuren in Form ihrer wasserlöslichen Alkali- oder Alkanolaminsalze oder auf Fettaminen, vorzugsweise in Form ihrer organischen oder anorganischen Salze.The chain lubricants hitherto used as lubricants are usually based on fatty acids in the form of their water-soluble alkali or alkanolamine salts or on fatty amines, preferably in the form of their organic or inorganic salts.
Während beide Substanzklassen in der Tauchschmierung problemlos anwendbar sind, zeigen sie in den heute üblichen zentralen Kettenschmiersystemen eine Reihe von Nachteilen. So beschreibt die
- 1. Es kommt zu einer Reaktion mit der Wasserhärte, also den Erdalkali-Ionen, und anderen Wasserinhaltsstoffen unter Bildung schwerlöslicher Metallseifen, den sogenannten primären Erdalkaliseifen.
- 2. Es kommt zu einer Reaktion zwischen diesen Schmiermitteln auf Seifenbasis und in Wasser oder dem abzufüllenden Gut gelöstem Kohlendioxid.
- 3. Die so erzeugte Anwendungslösung ist stets keimfördernd.
- 4. Bei Anwendung von hartem Wasser sind Ionenaustauscher zur Wasserenthärtung erforderlich, was eine zusätzliche Keimquelle bedeutet (und deshalb in der Praxis kaum anzutreffen ist), oder aber der Einsatz hoch komplexierungsmittelhaltiger Produkte, was wiederum ökologisch bedenklich ist, ist nötig.
- 5. Es kommt zu vermehrter Schaumbildung, was insbesondere Probleme am Bottle-Inspector (automatische Flaschenkontrolle) hervorrufen kann und eine stärkere Benetzung der Transportbehältnisse zur Folge hat.
- 6. Die meisten dieser Produkte sind lösungsmittelhaltig.
- 7. Die Reinigungswirkung dieser Produkte ist schlecht, so dass eine separate Reinigung notwendig ist.
- 8. Derartige Schmiermittelzubereitungen auf Seifenbasis zeigen ein pH-abhängiges Leistungsverhalten.
- 9. Schmiermittelzubereitungen auf Seifenbasis zeigen weiterhin eine Wassertemperatur-Abhängigkeit.
- 10. Schmiermittel auf Seifenbasis zeigen nur eine geringe Lagerstabilität, insbesondere bei niederen Temperaturen.
- 11. Das in vielen Produkten enthaltene EDTA (Ethylendiamintetraacetat) ist bekanntermaßen nur schlecht biologisch abbaubar.
- 12. Derartige Schmiermittelzubereitungen auf Seifenbasis sind nicht für alle Transportgüter aus Kunststoff geeignet, da es bei Anwendung dieser Mittel in vielen Fällen zu Spannungsrißkorrosionen am Transportgut kommt.
- 1. It comes to a reaction with the water hardness, ie the alkaline earth ions, and other water constituents to form sparingly soluble metal soaps, the so-called primary alkaline earth metal soaps.
- 2. There is a reaction between these soap based lubricants and carbon dioxide dissolved in water or the product to be bottled.
- 3. The application solution thus produced is always germ-promoting.
- 4. When using hard water ion exchangers are required for water softening, which means an additional source of germ (and therefore is hardly encountered in practice), or the use of highly complexing agent-containing products, which in turn is ecologically questionable, is necessary.
- 5. It comes to increased foaming, which in particular can cause problems with the bottle inspector (automatic bottle control) and has a stronger wetting of the transport containers result.
- 6. Most of these products contain solvents.
- 7. The cleaning effect of these products is poor, so that a separate cleaning is necessary.
- 8. Such soap-based lubricant formulations exhibit pH-dependent performance.
- 9. Soap based lubricant formulations continue to exhibit water temperature dependence.
- 10. Soap-based lubricants show only a short storage stability, especially at low temperatures.
- 11. The EDTA (ethylene diamine tetraacetate) found in many products is known to be poorly biodegradable.
- 12. Such soap-based lubricant preparations are not suitable for all plastic transport goods, since in many cases, when these agents are used, stress corrosion cracking occurs on the transported goods.
Neben Schmiermitteln auf Seifenbasis werden hauptsächlich solche auf Basis von Fettaminen verwendet. So beschreibt die
Aus der
- R1 eine gesättigte oder ungesättigte, verzweigte oder lineare Alkylgruppe mit 8 bis 22 C-Atomen;
- R2 Wasserstoff, eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 C-Atomen oder - A-NH2;
- A eine lineare oder verzweigte Alkylengruppe mit 1 bis 8 C-Atomen; und
- A1 eine lineare oder verzweigte Alkylengruppe mit 2 bis 4 C-Atomen bedeutet.
- R 1 is a saturated or unsaturated, branched or linear alkyl group having 8 to 22 C atoms;
- R 2 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 C atoms or --A-NH 2 ;
- A is a linear or branched alkylene group having 1 to 8 C atoms; and
- A 1 is a linear or branched alkylene group having 2 to 4 carbon atoms.
Darüber hinaus sind aus der
Aus der
Seifenfreie Schmiermittel auf der Basis von amphoteren Verbindungen, primären, sekundären und/oder tertiären Aminen und/oder Salzen derartiger Amine der allgemeinen Formel (I), (IIa), (IIb), (IIIa), (IIIb), (IIIc), (IVa) und (IVb)
R4-NH-R5 (IIa)
R4-N+H2-R5 X- (IIb)
R4-NH-(CH2)3NH2 (IIIa)
R4-NH-(CH2)3N+H3 X- (IIIb)
R4-N+H2-(CH2)3-N+H3 2X- (IIIc)
R4-NR7R8 (IVa)
und/oder
R4-N+HR7R8 X- (IVb)
wobei
- R
- für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 22 C-Atomen, der gegebenenfalls durch -OH,-NH2, -NH-, -CO-, -(CH2CH2O)l- oder -(CH2CH2CH2O)l- substituiert sein kann,
- R1
- für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, einen Hydroxyalkylrest mit 1 bis 4 C-Atomen oder einen Rest -R3COOM
- R2
- nur für den Fall, dass M eine negative Ladung darstellt für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen,
- R3
- für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 1 bis 12 C-Atomen, der gegebenenfalls durch -OH,-NH2, -NH-, -CO-, -(CH2CH2O)l- oder -(CH2CH2CH2O)l- substituiert sein kann,
- R4
- für einen substituierten oder unsubstituierten, linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen- und/oder Carboxyrest aufweisen kann, einen substituierten oder unsubstituierten Phenylrest, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen-, Carboxy- und/oder einen linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen aufweisen kann,
- R5
- für Wasserstoff oder - unabhängig von R4 - für einen Rest R4,
- X-
- für ein Anion aus der Gruppe Amidosulfonat, Nitrat, Halogenid, Sulfat, Hydrogencarbonat, Carbonat, Phosphat oder R6-COO- steht, wobei
- R6
- für Wasserstoff, einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann, steht, und
- R7
- und R8 jeweils unabhängig voneinander für einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder
einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann, - M
- für Wasserstoff, Alkalimetall, Ammonium, einen Alkylrest mit 1 bis 4 C-Atomen, einen Benzylrest oder eine negative Ladung,
- n
- für eine ganze Zahl im Bereich von 1 bis 12,
- m
- für eine ganze Zahl im Bereich von 0 bis 5 und
- l
- für eine Zahl im Bereich von 0 bis 5 steht,
Soap-free lubricants based on amphoteric compounds, primary, secondary and / or tertiary amines and / or salts of such amines of the general formula (I), (IIa), (IIb), (IIIa), (IIIb), (IIIc) (IVa) and (IVb)
R 4 -NH-R 5 (IIa)
R 4 -N + H 2 -R 5 X - (IIb)
R 4 -NH- (CH 2 ) 3 NH 2 (IIIa)
R 4 -NH- (CH 2 ) 3 N + H 3 X - (IIIb)
R 4 -N + H2- (CH 2 ) 3 -N + H 3 2X - (IIIc)
R 4 -NR 7 R 8 (IVa)
and or
R 4 -N + HR 7 R 8 X - (IVb)
in which
- R
- for a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, optionally substituted by -OH, -NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) l - or - (CH 2 CH 2 CH 2 O) l - may be substituted,
- R 1
- is hydrogen, an alkyl radical having 1 to 4 C atoms, a hydroxyalkyl radical having 1 to 4 C atoms or a radical -R 3 COOM
- R 2
- only in the case that M represents a negative charge for hydrogen, an alkyl radical having 1 to 4 C atoms, or a hydroxyalkyl radical having 1 to 4 C atoms,
- R 3
- for a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 C atoms, optionally substituted by -OH, -NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) l - or - (CH 2 CH 2 CH 2 O) l - may be substituted,
- R 4
- for a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, which may have as substituents at least one amine, imine, hydroxyl, halogen and / or carboxy radical, a substituted or unsubstituted phenyl radical which may have as substituents at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms,
- R 5
- is hydrogen or, independently of R 4 , is a radical R 4 ,
- X -
- represents an anion from the group amidosulfonate, nitrate, halide, sulfate, bicarbonate, carbonate, phosphate or R 6 -COO - , wherein
- R 6
- is hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have as substituents at least one hydroxyl, amine or imine radical, or a substituted or unsubstituted phenyl radical . which may have as substituents an alkyl radical having 1 to 20 carbon atoms, is, and
- R 7
- and R 8 each independently represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have as substituents at least one hydroxyl, amine or imine radical, or
a substituted or unsubstituted phenyl radical which may have as substituents an alkyl radical having 1 to 20 C atoms, - M
- is hydrogen, alkali metal, ammonium, an alkyl radical having 1 to 4 C atoms, a benzyl radical or a negative charge,
- n
- for an integer in the range of 1 to 12,
- m
- for an integer in the range of 0 to 5 and
- l
- is a number in the range of 0 to 5,
Die
- a) einer oder mehrerer Verbindungen der Formel
- R1 für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 22 C-Atomen, der gegebenenfalls durch -OH, -NH2, -NH-, -CO-, Halogen oder einen Carboxylrest substituiert sein kann,
- R2 für einen Carboxylrest mit 2 bis 7 C-Atomen,
- M für Wasserstoff, Alkalimetall, Ammonium, einen Alkylrest mit 1 bis 4 C-Atomen oder einen Benzylrest und
- n für eine ganze Zahl im Bereich von 1 bis 6 steht,
- b) wenigstens eine organische Carbonsäure ausgewählt aus einbasigen oder mehrbasigen, gesättigten oder einfach oder mehrfach ungesättigten Carbonsäuren mit 2 bis 22 C-Atomen,
- c) gegebenenfalls Wasser und Zusatz- und/oder Hilfsstoffe.
- a) one or more compounds of the formula
- R 1 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 C atoms, which may optionally be substituted by -OH, -NH 2 , -NH-, -CO-, halogen or a carboxyl radical,
- R 2 is a carboxyl radical having 2 to 7 C atoms,
- M is hydrogen, alkali metal, ammonium, an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and
- n is an integer in the range of 1 to 6,
- b) at least one organic carboxylic acid selected from monobasic or polybasic, saturated or mono- or polyunsaturated carboxylic acids having 2 to 22 C atoms,
- c) optionally water and additives and / or auxiliaries.
Die
Gemäß einer bevorzugten Ausführungsform der
R-A-(CH2)k-NH-[(CH2)l-NH]y-(CH2)m-NH2 · (H+X-)n
wobei
- R
- ein substituierter oder unsubstituierter, linearer oder verzweigter, gesättigter oder einfach oder mehrfach ungesättigter Alkylrest mit 6 bis 22 C-Atomen, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen und Carboxy, oder
ein substituierter oder unsubstituierter Phenylrest, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen, Carboxy und einem linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, ist; - A
- entweder für -NH- oder für -O- steht,
- X-
- ein Anion einer anorganischen oder organischen Säure bedeutet,
- k, l, m
- unabhängig voneinander eine ganze Zahl im Bereich von 1 bis 6 ist;
- y
- im Falle A = -NH- 0, 1, 2 oder 3 und
im Falle A = -O- 1, 2, 3 oder 4 ist, - n
- eine ganze Zahl von 0 bis 6 ist.
RA- (CH 2 ) k -NH - [(CH 2 ) 1 -NH] y - (CH 2 ) m -NH 2. (H + X - ) n
in which
- R
- a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 C atoms, wherein the substituents are selected from amino, imino, hydroxy, halogen and carboxy, or
a substituted or unsubstituted phenyl radical wherein the substituents are selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms; - A
- is either -NH- or -O-,
- X -
- an anion of an inorganic or organic acid means
- k, l, m
- independently is an integer in the range of 1 to 6;
- y
- in the case of A = -NH- 0, 1, 2 or 3 and
in case A = -O- 1, 2, 3 or 4, - n
- is an integer from 0 to 6.
Die Anmeldung
Dabei werden als besonders bevorzugt Polyhydroxyverbindungen genannt, die ausgewählt sind aus Alkandiolen oder Alkantriolen, ganz besonders bevorzugt Glycerin, oder deren Polymere sowie deren Ester und Ether.Particular preference is given to polyhydroxy compounds which are selected from alkanediols or alkanetriols, very particularly preferably glycerol, or their polymers and their esters and ethers.
Aus Sicht des Anwenders ergibt sich jedoch bei den eingesetzten Kettengleitmitteln immer wieder das Problem, dass sie entweder zu schlecht auf den Ketten haften bleiben oder zu stark auf die Ketten aufziehen.From the point of view of the user, however, the problem with the chain lubricants used is that they either stick too badly on the chains or pull on the chains too much.
Für den Fall, dass Kettengleitmittel zu schlecht auf den Ketten haften, tropfen sie bereits kurz nach der Applikation auf den Boden mit dem Ergebnis, dass die Schmierwirkung auf den mehrere Meter langen Ketten stark von der Nähe zu der Dosierstelle abhängt. Das gleiche Problem ergibt sich an den Stellen, wo die Gefahr besteht, dass durch verschüttetes Getränk die Schmierschicht schnell von den Oberflächen entfernt wird. Die Folge ist, dass es je nach Bereich zu sehr unterschiedlichen Schmierqualitäten kommen kann. In kritischen Bereichen führt dies häufig zu Umfallen der Flaschen bis hin zur Unterbrechung des Abfüllbetriebs.In the event that chain lubricants adhere too badly to the chains, they drip on the ground shortly after application, with the result that the lubricating effect on the chains several meters long depends strongly on the proximity to the metering point. The same problem arises where there is a risk that the smear layer will be quickly removed from the surfaces by spilled beverage. The consequence is that, depending on the area, very different lubricating qualities can occur. In critical areas, this often leads to dropping of the bottles up to the interruption of the filling operation.
Für den Fall, dass Kettengleitmittel sehr gut auf den Ketten haften, wie dies beispielsweise bei den sehr gut benetzenden Fluortensiden der Fall ist, bildet sich auf den Transportketten ein fest anhaftender Film, der durch Spülen mit Wasser nicht einfach zu entfernen ist.In the event that chain lubricants adhere very well to the chains, as is the case with the very well-wetting fluorosurfactants, for example, forms the transport chains a firmly adhering film that is not easy to remove by rinsing with water.
In diesem Film können sich Rückstände und Abriebstoffe sammeln und zu Hygiene- und Betriebsstörungen im Betrieb führen.
Dementsprechend war es Aufgabe der vorliegenden Erfindung Kettengleitmittel zur Verfügung zu stellen, die einerseits gutes Haftvermögen auf den Ketten besitzen, gute Schmiereigenschaften aufweisen und einen Film bilden, der sich bei Bedarf wieder einfach von den Ketten entfernen läßt. Außerdem sollten derartige Kettengleitmittel in lagerstabiler Formulierung vorliegen. Überraschenderweise läßt sich obiges Problem durch lagerstabile O/W-Emulsionen lösen.In this film, residues and abrasives can accumulate and lead to hygiene and operational problems in operation.
Accordingly, it was an object of the present invention to provide chain lubricants are available, on the one hand have good adhesion to the chains, have good lubricating properties and form a film that can be easily removed when needed again from the chains. In addition, such chain lubricants should be in storage stable formulation. Surprisingly, the above problem can be solved by storage-stable O / W emulsions.
Dementsprechend ist Gegenstand der vorliegenden Erfindung die Verwendung einer O/W-Emulsion in konzentrierter Form oder nach Verdünnen mit Wasser zum Schmieren von Transportbändern in Lebensmittelbetrieben.Accordingly, the subject of the present invention is the use of an O / W emulsion in concentrated form or after dilution with water for lubricating conveyor belts in food processing plants.
Es ist bekannt, dass Öl-in-Wasser-Emulsionen, fortan O/W-Emulsionen genannt, die mit nichtionischen Emulgatoren hergestellt und stabilisiert sind, beim Erwärmen eine Phaseninversion erleiden. Unter diesem Vorgang der Phaseninversion ist zu verstehen, dass bei höheren Temperaturen die äußere, wässrige Phase zur inneren Phase wird. Dieser Vorgang ist in der Regel reversibel, das heißt, dass sich beim Abkühlen wieder der ursprüngliche Emulsionstyp zurückbildet. Es ist auch bekannt, dass die Lage der Phaseninversionstemperatur von vielen Faktoren abhängt, zum Beispiel von der Art und dem Phasenvolumen der Ölkomponente, von der Hydrophilie und der Struktur des Emulgators oder der Zusammensetzung des Emulgatorsystems, vergleiche zum Beispie!
In den genannten Druckschriften wurden jedoch nur Emulsionen untersucht, deren Ölphase ganz oder überwiegend aus unpolaren Kohlenwasserstoffen besteht. Demgegenüber verhalten sich entsprechende Emulsionen, deren Ölkomponente ganz oder überwiegend aus polaren Estern oder Triglyceridölen besteht, anders entweder werden (a) trotz einer Phaseninversion keine feinteiligen, blauen Emulsionen gebildet, sondern grobdisperse weiße Emulsionen oder aber es findet (b) im Temperaturbereich bis 100 °C überhaupt keine Phaseninversion statt.In the cited documents, however, only emulsions were examined whose oil phase consists wholly or predominantly of nonpolar hydrocarbons. In contrast, corresponding emulsions whose oil component consists wholly or predominantly of polar esters or triglyceride oils, either (a) despite a phase inversion no finely divided, blue emulsions are formed, but coarsely dispersed white emulsions or it finds (b) in the temperature range up to 100 ° C no phase inversion at all.
Die deutsche Patentanmeldung
In der
Dabei wurde gefunden, dass O/W-Emulsionen auf Basis polarer Ölkörper und nichtionsicher Emulgatoren dann besonders feinteilig und langzeitstabil sind, wenn man eine Mischung aus polarem Öl, nichtionischem Emulgator und einem speziellen Grenzflächen-Moderator auf eine Temperatur innerhalb oder oberhalb des Phaseninversions-Temperaturbereiches erhitzt - oder die Emulsion bei dieser Temperatur herstellt - und dann die Emulsion auf eine Temperatur unterhalb des Phaseninversion-Temperturbereiches abkühlt und gegebenenfalls mit Wasser weiter verdünnt.It has been found that O / W emulsions based on polar oil bodies and non-ionic emulsifiers are then particularly finely divided and long-term stable when a mixture of polar oil, nonionic emulsifier and a special interface moderator to a temperature within or above the phase inversion temperature range heated - or the emulsion prepares at this temperature - and then the emulsion is cooled to a temperature below the Phaseninversion-Temperturbereiches and optionally further diluted with water.
In der
- (A) 10 bis 90 Gew.-% eines polaren Ölkörpers mit
- (B) 0,5 bis 30 Gew.-% eines nichtionscihen Emulgators mit einem HLB-Wert von 10 bis 18 und
- (C) 0 bis 30 Gew.-% eines Co-Emulgators aus der Gruppe der Fettalkohole mit 12 bis 22 C-Atomen oder der Partialester von Polyolen mit 3 bis 6 C-Atomen mit Fettsäuren mit 12 bis 22 C-Atomen und
- (D) 0,01 bis 50 Gew.-% eines Grenzflächen-Moderators, der ausgewählt ist aus der Gruppe der Tocopherole, der Guerbetalkohle mit 16 bis 20 C-Atomen oder eines Steroids mit 1 bis 3 OH-Gruppen
- (A) 10 to 90 wt .-% of a polar oil body with
- (B) 0.5 to 30% by weight of a nonionic emulsifier having an HLB of 10 to 18 and
- (C) 0 to 30 wt .-% of a co-emulsifier from the group of fatty alcohols having 12 to 22 carbon atoms or the partial esters of polyols having 3 to 6 carbon atoms with fatty acids having 12 to 22 carbon atoms and
- (D) 0.01 to 50% by weight of an interfacial moderator selected from the group of tocopherols, Guerbetal coal having 16 to 20 carbon atoms or a steroid having 1 to 3 OH groups
Dieses Verfahren hat den Vorteil, dass besonders feinteilige Emulsionen erhalten werden, die eine ausgezeichnete Lagerstabilität aufweisen. Im Vergleich zum bis dahin bekannten Stand der Technik, z.B. der
Die Öl-in-Wasser-Emulsionen, hergestellt nach dem PIT-Verfahren finden Anwendung z.B. als Haut- und Körperpflegemittel, als Kühlschmiermittel oder als Textil- und Faserhilfsmittel. Besonders bevorzugt sind sie bei Verfahren zur Herstellung emulsionsförmiger Zubereitungen für die Haut- und Haarbehandlung.The oil-in-water emulsions prepared by the PIT method find use, e.g. as a skin and body care product, as a cooling lubricant or as a textile and fiber auxiliary. They are particularly preferred in processes for the preparation of emulsion-like preparations for skin and hair treatment.
In diesem Zusammenhang sei auf das deutsche Patent
Im derzeit zugänglichen Stand der Technik ist eine erfindungsgemäße Verwendung von O/W-Emulsionen weder offenbart, noch wird in irgendwelcher Form darauf hingewiesen.In the currently available prior art, a use according to the invention of O / W emulsions is neither disclosed nor mentioned in any form.
Die Erfindung bezieht sich auf die folgenden Aspekte.
- 1. Verwendung einer O/W-Emulsion in konzentrierter Form oder nach Verdünnen mit Wasser zum Schmieren von Transportbändern in Lebensmittelbetrieben.
- 2. Verwendung nach Aspekt 1, dadurch gekennzeichnet, dass die O/W-Emulsion eine PIT-Emulsion ist,
- 3. Verwendung nach einem der Aspekte 1 oder 2, dadurch gekennzeichnet, dass die O/W-Emulsion wenigstens einen Wachsester enthält.
- 4. Verwendung nach Aspekt 3, dadurch gekennzeichnet, dass die O/W-Emulsion mindestens eine weitere Komponente ausgewählt aus den Gruppen der
- (a) Triglyceride,
- (b) Partialglyceride, oder
- (c) Fettalkoholpolyglykolether
- 5. Verwendung nach einem der Aspekte 3 oder 4, dadurch gekennzeichnet, dass man Wachsester der Formel (1) einsetzt,
R1CO-OR2 (1)
in der R1CO für einen gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen und R2 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen steht. - 6. Verwendung nach einem der Aspekte 4 oder 5, dadurch gekennzeichnet, dass unter a) Triglyceride der Formel (2) zu verstehen sind,
- 7. Verwendung nach einem oder mehreren der Aspekte 4 bis 6, dadurch gekennzeichnet, dass unter b) Partialglyceride der Formel (3) zu verstehen sind,
- 8. Verwendung nach einem oder mehreren der Aspekte 4 bis 7, dadurch gekennzeichnet, dass unter c) Fettalkoholpolyglycolether der Formel (4) zu verstehen sind,
R9O(CH2CH2O)qH (4)
in der R9 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen und q für Zahlen von 1 bis 50 steht. - 9. Verwendung nach einem oder mehreren der Aspekte 4 bis 8, dadurch gekennzeichnet, dass man O/W-Emulsionen, enthaltend
- (x) 1 bis 50 Gew.-% Wachsester,
- (a) 0,04 bis 10 Gew.-% Triglyceride,
- (b) 0,04 bis 10 Gew.-% Partialglyceride und
- (c) 0,04 bis 20 Gew.-% Fettalkoholpolyglycolether
- 10. Verwendung nach einem oder mehreren der Aspekte 1 bis 9, dadurch gekennzeichnet, dass in der genannten O/W-Emulsion zumindestens eine alkoholische Komponente ausgewählt aus Monohydroxy-, Dihydroxy- und Trihydroxy-Verbindungen, in Kombination mit mindestens einer weiteren Komponente ausgewählt aus
- (d) stickstoffhaltigen, aliphatischen, organischen Verbindungen mit weniger als 10 C-Atomen im Molekül und/oder
- (e) einer organischen Carbonsäure mit 1 bis 10 C-Atomen im Molekül, vorliegt.
- 11. Verwendung nach Aspekt 10, dadurch gekennzeichnet, dass der Anteil der genannten alkoholischen Komponente, bezogen auf die gesamte O/W-Emulsion, größer als 20 Gew.-% ist.
- 12. Verwendung nach Aspekt 11, dadurch gekennzeichnet, dass als genannte stickstoffhaltige Verbindung (d) eine Verbindung der Formel 5
- 13. Verwendung nach einem oder mehreren der Aspekte 10 bis 12, dadurch gekennzeichnet, dass der Anteil an stickstoffhaltiger Verbindung (d), bezogen auf das gesamte Konzentrat, 0,1 bis 20 Gew.-% beträgt.
- 14. Verwendung nach einem oder mehreren der Aspekte 10 bis 13, dadurch gekennzeichnet, dass der Anteil der genannten organischen Carbonsäure (e), bezogen auf das gesamte Konzentrat, 0,1 bis 20 Gew.-% beträgt.
- 15. Verwendung nach einem der Aspekte 1 bis 14, dadurch gekennzeichnet, daß in der genannten O/W-Emulsion zumindest eine weitere Komponente ausgewählt aus den Kettengleitmittel-Wirkstoffen der allgemeinen Formel (I), (II)a, (IIb), (IIIa), (IIIb), (IIIc), (IVa), (IVb) und/oder (V)
R4-NH-R5 (IIa)
R4-N+H2-R5 X- (IIb)
R4-NH-(CH2)3NH2 (IIIa)
R4-NH-(CH2)3N+H3 X- (IIIb)
R4-N+H2-(CH2)3-N+H3 2X- (IIIc)
R4-NR7R8 (IVa)
und/oder
R4-N+HR7R8 X- (IVb)
wobei- Rfür einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 6 bis 22 C-Atomen, der gegebenenfalls durch -OH, - NH2, -NH-, -CO-, -(CH2CH2O)l- oder -(CH2CH2CH2O)l- substituiert sein kann,
- R1 für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, einen Hydroxyalkylrest mit 1 bis 4 C-Atomen oder einen Rest -R3COOM
- R2 nur für den Fall, dass M eine negative Ladung darstellt für Wasserstoff, einen Alkylrest mit 1 bis 4 C-Atomen, oder einen Hydroxyalkylrest mit 1 bis 4 C-Atomen,
- R3 für einen gesättigten oder einfach oder mehrfach ungesättigten, linearen oder verzweigten Alkylrest mit 1 bis 12 C-Atomen, der gegebenenfalls durch-OH, -NH2, -NH-, -CO-, -(CH2CH2O)l- oder -(CH2CH2CH2O)l- substituiert sein kann,
- R4 für einen substituierten oder unsubstituierten, linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen- und/oder Carboxyrest aufweisen kann,
- einen substituierten oder unsubstituierten Phenylrest, der als Substituenten mindestens einen Amin-, Imin-, Hydroxy-, Halogen-, Carboxy- und/oder einen linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen aufweisen kann,
- R5 für Wasserstoff oder - unabhängig von R4 - für einen Rest R4,
- X- für ein Anion aus der Gruppe Amidosulfonat, Nitrat, Halogenid, Sulfat, Hydrogencarbonat, Carbonat, Phosphat oder R6-COO- steht, wobei
- R6 für Wasserstoff, einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann, steht, und
- R7 und R8 jeweils unabhängig voneinander für einen substituierten oder unsubstituierten, linearen oder verzweigten Alkylrest mit 1 bis 20 C-Atomen oder Alkenylrest mit 2 bis 20 C-Atomen, die als Substituenten mindestens einen Hydroxy-, Amin- oder Iminrest aufweisen können, oder
- einen substituierten oder unsubstituierten Phenylrest, der als Substituenten einen Alkylrest mit 1 bis 20 C-Atomen aufweisen kann,
- M für Wasserstoff, Alkalimetall, Ammonium, einen Alkylrest mit 1 bis 4 C-Atomen, einen Benzylrest oder eine negative Ladung,
- n für eine ganze Zahl im Bereich von 1 bis 12,
- m für eine ganze Zahl im Bereich von 0 bis 5 und
- l für eine Zahl im Bereich von 0 bis 5
- steht, sowie
R-A-(CH2)k-NH-[(CH2)l-NH]y-H · (H+X-)n (V)
wobei- Rein substituierter oder unsubstituierter, linearer oder verzweigter, gesättigter oder einfach oder mehrfach ungesättigter Alkylrest mit 6 bis 22 C-Atomen, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen und Carboxy, oder
- ein substituierter oder unsubstituierter Phenylrest, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen, Carboxy und einem linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, ist;
- A entweder für -NH- oder für -O- steht,
- X- ein Anion einer anorganischen oder organischen Säure bedeutet,
- k, l unabhängig voneinander eine ganze Zahl im Bereich von 1 bis 6 ist;
- y O, 1, 2, 3, 4 oder 5 ist,
- n eine ganze Zahl von 0 bis 6 ist,
- enthalten sind.
- 16. Verwendung nach einem der Aspekte 1 bis 15, dadurch gekennzeichnet, dass der Anteil der wässrigen Phase in der O/W-Emulsion größer als 95 Gew.%, bezogen auf die gesamte O/W-Emulsion, ist.
- 17. Verwendung nach einem oder mehreren der Aspekte 1 bis 15, dadurch gekennzeichnet, dass man O/W-Emulsionen, enthaltend
- (x) 25 bis 50 Gew.-% Wachsester,
- (a) 1 bis 10 Gew.-% Triglyceride,
- (b) 1 bis 10 Gew.-% Partialglyceride und
- (c) 1 bis 20 Gew.-% Fettalkoholpolyglycolether
- 18. Verwendung nach einem oder mehreren der Aspekte 1 bis 17, dadurch gekennzeichnet, dass die genannte O/W-Emulsion zusätzlich mindestens eine antimikrobielle Komponente ausgewählt aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, Iodo-2-propynyl-butyl-carbamat, Iod, Iodophore, Peroxide, Persäuren enthält, wobei die genannten Komponenten unterschiedlich von den in den Aspekten 2 bis 15 aufgeführten Komponenten sind.
- 19. Verwendung nach einem oder mehreren der Aspekte 1 bis 18, dadurch gekennzeichnet, dass die genannte O/W-Emulsion unmittelbar vor dem Aufbringen auf die Bänder der genannten Transportbandanlage erzeugt wird.
- 20. Verwendung nach einem oder mehreren der Aspekte 1 bis 19, dadurch gekennzeichnet, dass die genannte O/W-Emulsion oder deren verdünnte Lösung zum Transport von Kunststoff-, Karton-, Metall- oder Glas-Gebinden eingesetzt wird.
- 21. Verwendung nach einem oder mehreren der Aspekte 1 bis 20, dadurch gekennzeichnet, dass die O/W-Emulsion direkt, ohne vorheriges Verdünnen über eine Applikationsvorrichtung auf die Bänder der Transportanlage aufgebracht wird.
- 22.Verwendung nach einem oder mehreren der Aspekte 1 bis 20, dadurch gekennzeichnet, dass die O/W-Emulsion in der Transportanlage mit Wasser verdünnt wird, bevor sie über eine Applikationsvorrichtung auf die Bänder der Transportanlage aufgebracht wird.
- 23. Verwendung nach Aspekt 22, dadurch gekennzeichnet, dass die O/W-Emulsion um einen Verdünnungsfaktor verdünnt wird, der zwischen 20.000 und 100 liegt.
- 24.Verwendung nach einem oder mehreren der Aspekte 21 bis 23, dadurch gekennzeichnet, dass die Applikationsvorrichtung während der Applikation in direktem Kontakt mit den zu schmierenden Oberflächen steht.
- 25. Verwendung nach einem oder mehreren der Aspekte 21 bis 23, dadurch gekennzeichnet, dass als Applikationsvorrichtung eine Sprühvorrichtung verwendet wird.
- 26. Schmiermittelkonzentrat enthaltend einen Wachsester, zur Schmierung von Transportbandanlagen in Lebensmittelbetrieben, dadurch gekennzeichnet, dass das Schmiermittelkonzentrat als O/W-Emulsion vorliegt,
- 27. Schmiermittelkonzentrat nach Aspekt 26, dadurch gekennzeichnet, dass die O/W-Emulsion mindestens eine weitere Komponente ausgewählt aus den Gruppen der
- a) Triglyceride,
- b) Partialglyceride, oder
- c) Fettalkoholpolyglykolether
- 28.Schmiermittelkonzentrat nach Aspekt 27, dadurch gekennzeichnet, dass die O/W-Emulsion
- (x) 1 bis 50 Gew.-% Wachsester,
- (a) 0,04 bis 10 Gew.-% Triglyceride,
- (b) 0,04 bis 10 Gew.-% Partialglyceride und
- (c) 0,04 bis 20 Gew.-% Fettalkoholpolyglycolether
- 29. Schmiermittelkonzentrat nach Aspekt 28, dadurch gekennzeichnet, dass die O/W-Emulsion
- (x) 25 bis 50 Gew.-% Wachsester,
- (a) 1 bis 10 Gew.-% Triglyceride,
- (b) 1 bis 10 Gew.-% Partialglyceride und
- (c) 1 bis 20 Gew.-% Fettalkoholpolyglycolether
- 1. Use of an O / W emulsion in concentrated form or after dilution with water for lubricating conveyor belts in food processing plants.
- 2. Use according to aspect 1, characterized in that the O / W emulsion is a PIT emulsion,
- 3. Use according to one of aspects 1 or 2, characterized in that the O / W emulsion contains at least one wax ester.
- 4. Use according to aspect 3, characterized in that the O / W emulsion at least one further component selected from the groups of
- (a) triglycerides,
- (b) partial glycerides, or
- (c) fatty alcohol polyglycol ether
- 5. Use according to one of the aspects 3 or 4, characterized in that wax esters of the formula (1) are used,
R 1 CO-OR 2 (1)
in which R 1 CO is a saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms and R 2 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms. - 6. Use according to one of the aspects 4 or 5, characterized in that a) triglycerides of the formula (2) are to be understood,
- 7. Use according to one or more of aspects 4 to 6, characterized in that b) partial glycerides of the formula (3) are to be understood,
- 8. Use according to one or more of aspects 4 to 7, characterized in that c) fatty alcohol polyglycol ethers of the formula (4) are to be understood,
R 9 O (CH 2 CH 2 O) q H (4)
in which R 9 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q is a number from 1 to 50. - 9. Use according to one or more of aspects 4 to 8, characterized in that O / W emulsions containing
- (x) 1 to 50% by weight of wax ester,
- (a) 0.04 to 10% by weight of triglycerides,
- (b) 0.04 to 10% by weight of partial glycerides and
- (c) 0.04 to 20% by weight of fatty alcohol polyglycol ether
- 10. Use according to one or more of aspects 1 to 9, characterized in that in said O / W emulsion at least one alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds, in combination with at least one further component selected from
- (d) nitrogen-containing, aliphatic, organic compounds having less than 10 C atoms in the molecule and / or
- (E) an organic carboxylic acid having 1 to 10 carbon atoms in the molecule, is present.
- 11. Use according to aspect 10, characterized in that the proportion of said alcoholic component, based on the total O / W emulsion, greater than 20 wt .-% is.
- 12. Use according to aspect 11, characterized in that as said nitrogen-containing compound (d) is a compound of formula 5
- 13. Use according to one or more of aspects 10 to 12, characterized in that the proportion of nitrogen-containing compound (d), based on the total concentrate, 0.1 to 20 wt .-% is.
- 14. Use according to one or more of aspects 10 to 13, characterized in that the proportion of said organic carboxylic acid (s), based on the total concentrate, 0.1 to 20 wt .-% is.
- 15. Use according to one of aspects 1 to 14, characterized in that in said O / W emulsion at least one further component selected from the chain lubricant active compounds of the general formula (I), (II) a, (IIb), ( IIIa), (IIIb), (IIIc), (IVa), (IVb) and / or (V)
R 4 -NH-R 5 (IIa)
R 4 -N + H 2 -R 5 X - (IIb)
R 4 -NH- (CH 2 ) 3 NH 2 (IIIa)
R 4 -NH- (CH 2 ) 3 N + H 3 X - (IIIb)
R 4 -N + H2- (CH 2 ) 3 -N + H 3 2X - (IIIc)
R 4 -NR 7 R 8 (IVa)
and or
R 4 -N + HR 7 R 8 X - (IVb)
in which- R is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 6 to 22 carbon atoms, optionally substituted by -OH, - NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) l - or - (CH 2 CH 2 CH 2 O) l - may be substituted,
- R 1 is hydrogen, an alkyl radical having 1 to 4 C atoms, a hydroxyalkyl radical having 1 to 4 C atoms or a radical -R 3 COOM
- R 2 only in the event that M represents a negative charge for hydrogen, an alkyl radical having 1 to 4 carbon atoms, or a hydroxyalkyl radical having 1 to 4 carbon atoms,
- R 3 is a saturated or mono- or polyunsaturated, linear or branched alkyl radical having 1 to 12 C atoms, optionally substituted by -OH, -NH 2 , -NH-, -CO-, - (CH 2 CH 2 O) l - or - (CH 2 CH 2 CH 2 O) l - may be substituted,
- R 4 is a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 C atoms, which may have as substituents at least one amine, imine, hydroxyl, halogen and / or carboxy radical,
- a substituted or unsubstituted phenyl radical which may have as substituents at least one amine, imine, hydroxyl, halogen, carboxy and / or a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms,
- R 5 is hydrogen or, independently of R 4 , is a radical R 4 ,
- X - represents an anion from the group amidosulfonate, nitrate, halide, sulfate, bicarbonate, carbonate, phosphate or R 6 -COO - , wherein
- R 6 is hydrogen, a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have as substituents at least one hydroxyl, amine or imine radical, or a substituted or unsubstituted phenyl radical which may have as substituents an alkyl radical having 1 to 20 carbon atoms, is, and
- R 7 and R 8 each independently represent a substituted or unsubstituted, linear or branched alkyl radical having 1 to 20 C atoms or alkenyl radical having 2 to 20 C atoms, which may have as substituents at least one hydroxyl, amine or imine radical, or
- a substituted or unsubstituted phenyl radical which may have as substituents an alkyl radical having 1 to 20 C atoms,
- M is hydrogen, alkali metal, ammonium, an alkyl radical having 1 to 4 C atoms, a benzyl radical or a negative charge,
- n is an integer in the range of 1 to 12,
- m is an integer in the range of 0 to 5 and
- l is a number in the range of 0 to 5
- stands, as well
RA- (CH 2) k -NH - [(CH 2) l -NH] y -H · (H + X -) n (V)
in which- Purely substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms, where the substituents are selected from amino, imino, hydroxy, halogen and carboxy, or
- a substituted or unsubstituted phenyl radical wherein the substituents are selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms;
- A is either -NH- or -O-,
- X - an anion of an inorganic or organic acid means
- k, l is independently an integer in the range of 1 to 6;
- y is O, 1, 2, 3, 4 or 5,
- n is an integer from 0 to 6,
- are included.
- 16. Use according to one of aspects 1 to 15, characterized in that the proportion of the aqueous phase in the O / W emulsion is greater than 95 wt.%, Based on the total O / W emulsion.
- 17. Use according to one or more of aspects 1 to 15, characterized in that O / W emulsions containing
- (x) 25 to 50% by weight wax ester,
- (a) 1 to 10% by weight of triglycerides,
- (b) 1 to 10% by weight of partial glycerides and
- (c) 1 to 20% by weight of fatty alcohol polyglycol ether
- 18. Use according to one or more of aspects 1 to 17, characterized in that said O / W emulsion additionally comprises at least one antimicrobial component selected from the groups of alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls , Diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2 -propynyl-butyl-carbamate, iodine, iodophores, peroxides, peracids, said components being different from the components listed in aspects 2 to 15.
- 19. Use according to one or more of aspects 1 to 18, characterized in that said O / W emulsion is produced immediately prior to application to the belts of said conveyor belt system.
- 20. Use according to one or more of aspects 1 to 19, characterized in that said O / W emulsion or its dilute solution for the transport of plastic, cardboard, metal or glass containers is used.
- 21. Use according to one or more of aspects 1 to 20, characterized in that the O / W emulsion is applied directly without prior dilution via an application device on the belts of the transport system.
- 22.Use according to one or more of aspects 1 to 20, characterized in that the O / W emulsion is diluted in the transport system with water before it is applied via an application device on the belts of the transport system.
- 23. Use according to aspect 22, characterized in that the O / W emulsion is diluted by a dilution factor which is between 20,000 and 100.
- 24.Use according to one or more of aspects 21 to 23, characterized in that the application device during the application is in direct contact with the surfaces to be lubricated.
- 25. Use according to one or more of aspects 21 to 23, characterized in that a spraying device is used as the application device.
- 26. A lubricant concentrate containing a wax ester, for the lubrication of conveyor belts in food processing plants, characterized in that the lubricant concentrate is present as O / W emulsion,
- 27. lubricant concentrate according to aspect 26, characterized in that the O / W emulsion at least one further component selected from the groups of
- a) triglycerides,
- b) partial glycerides, or
- c) fatty alcohol polyglycol ether
- 28.The lubricant concentrate according to aspect 27, characterized in that the O / W emulsion
- (x) 1 to 50% by weight of wax ester,
- (a) 0.04 to 10% by weight of triglycerides,
- (b) 0.04 to 10% by weight of partial glycerides and
- (c) 0.04 to 20% by weight of fatty alcohol polyglycol ether
- 29. lubricant concentrate according to aspect 28, characterized in that the O / W emulsion
- (x) 25 to 50% by weight wax ester,
- (a) 1 to 10% by weight of triglycerides,
- (b) 1 to 10% by weight of partial glycerides and
- (c) 1 to 20% by weight of fatty alcohol polyglycol ether
In einer bevorzugten Ausführungsform der erfindungsgemäßen Verwendung enthält die O/W-Emulsion wenigstens einen Wachsester.In a preferred embodiment of the use according to the invention, the O / W emulsion contains at least one wax ester.
Unter Wachsestern sind Ester von langkettigen Carbonsäuren mit langkettigen Alkoholen zu verstehen, die vorzugsweise der Formel (1) folgen,
R1CO-OR2 (1)
in der R1CO für einen gesättigten und/oder ungesättigten Acylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und R2 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen steht. Typische Beispiele sind Ester von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolen-säure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen mit Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Lauryl-alkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearyl-alkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenylalkohol, Elaeostearyl-alkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen, Vorzugsweise werden Cetylpalmitat, Cetylstearat, Cetylisostearat, Cetyl-oleat, Cetylbehenat, Cetylerucat, Stearylpalmitat, Stearylstearat, Stearylisostearat, Stearyloleat, Stearylbehenat, Stearylerucat, Isosteraylpalmitat, Isostearylstearat, Isostearylisostearat, Isostearyloleat, Isostearylbehenat, Isostearylerucat, Oleylpalmitat, Oleylstearat, Oleylisostearat, Oleyloleat, Oleylbehenat, Oleylerucat, Behenylpalmitat, Behenylstearat, Behenylisostearat, Behenyloleat, Behenylbehenat, Behenyloleat sowie deren Mischungen eingesetzt. Weiterhin können als Wachsester auch Ester der genannten Alkohole mit Fruchtsäuren, also beispielsweise Äpfel- Wein- oder Citronensäure, Fruchtwachse sowie Siliconwachse eingesetzt werden.Wax esters are esters of long-chain carboxylic acids with long-chain alcohols, which preferably follow the formula (1),
R 1 CO-OR 2 (1)
in which R 1 CO is a saturated and / or unsaturated acyl radical having 6 to 22, preferably 12 to 18 carbon atoms and R 2 is an alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms. Typical examples are esters of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures with caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol Cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate , Stearyl erucate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl erucate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl oleate and mixtures thereof. Furthermore, as wax esters and esters of the alcohols mentioned with fruit acids, so for example, apple acids or citric acid, fruit waxes and silicone waxes can be used.
Die erfindungsgemäß zu verwendende O/W-Emulsion enthält vorzugsweise mindestens eine weitere Komponente ausgewählt aus den Gruppen der
- a) Triglyceride,
- b) Partialglyceride, oder
- c) Fettalkoholpolyglykolether, oder
- a) triglycerides,
- b) partial glycerides, or
- c) fatty alcohol polyglycol ethers, or
Unter Triglyceriden sind Stoffe der Formel (2) zu verstehen,
in der R3CO, R4CO und R5CO unabhängig voneinander für lineare oder verzweigte, gesättigte und/oder ungesättigte, gegebenenfalls hydroxy- und/oder epoxysubstituierte Acylreste mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen und die Summe (m+n+p) für 0 oder Zahlen von 1 bis 100, vorzugsweise 20 bis 80 steht. Die Triglyceride können natürlicher Herkunft sein oder auf synthetischem Wege herge-stellt werden. Vorzugsweise handelt es sich um hydroxy- und/oder epoxyfunktionalisierte Stoffe, wie beispielsweise Ricinusöl oder gehärtetes Ricinusöl, epoxidiertes Ricinusöl, Ringöffnungsprodukte von epoxidierten Ricinusölen unterschiedlicher Epoxidzahlen mit Wasser sowie Anlagerungsprodukten von durchschnittlich 1 bis 100, vorzugsweise 20 bis 80 und insbesondere 40 bis 60 Mol an diese genannten Triglyceride.in the R 3 CO, R 4 CO and R 5 CO independently represent linear or branched, saturated and / or unsaturated, optionally hydroxy- and / or epoxy-substituted acyl radicals having 6 to 22, preferably 12 to 18 carbon atoms and the sum (m + n + p) is 0 or numbers from 1 to 100, preferably 20 to 80. The triglycerides may be of natural origin or synthetically produced. Preference is given to hydroxy- and / or epoxy-functionalized substances, such as, for example, castor oil or hydrogenated castor oil, epoxidized castor oil, ring opening products of epoxidized castor oils of different epoxide numbers with water and addition products of on average from 1 to 100, preferably from 20 to 80 and in particular from 40 to 60 mol these triglycerides.
Partialglyceride sind Monoglyceride, Diglyceride und deren technische Gemische, die herstellungsbedingt noch geringe Mengen Triglyceride enthalten können. Die Partialglyceride folgen vorzugsweise der Formel (3),
Die erfindungsrelevanten Fettalkoholpolyglykolether entsprechen der Formel (4),
R9O(CH2CH2O)qH (4)
in der R9 für einen linearen oder verzweigten Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoff-atomen und q für Zahlen von 1 bis 50 steht. Typische Beispiele sind Anlagerungsprodukte von durchschnittliche 1 bis 50, vorzugsweise 5 bis 25 an Capronalkohol, Caprylalkohol, 2-Ethylhexylalkohol, Caprinalkohol, Laurylalkohol, Isotridecylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Linolylalkohol, Linolenyl-alkohol, Elaeostearylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol und Brassidylalkohol sowie deren technische Mischungen. Die Tenside können dabei sowohl eine konventionell breite als auch eine eingeengte Homologenverteilung aufweisen. Besonders bevorzugt sind Anlagerungsprodukte von durchschnittlich 10 bzw. 20 Mol Ethylenoxid an Cetearylalkohol, Stearylalkohol und/ oder Behenylalkohol.The fatty alcohol polyglycol ethers according to the invention correspond to the formula (4) ,
R 9 O (CH 2 CH 2 O) q H (4)
in which R 9 is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and q is a number from 1 to 50. Typical examples are adducts of an average of 1 to 50, preferably 5 to 25, of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol , Elaeostearylalkohol, arachyl alcohol, Gadoleylalkohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. The surfactants may have both a conventional broad and a narrow homolog distribution. Particularly preferred are addition products of on average 10 or 20 moles of ethylene oxide to cetearyl alcohol, stearyl alcohol and / or behenyl alcohol.
Als weitere Komponenten kommen Co-Emulgatoren wie beispielsweise nichtionogene Tenside aus mindestens einer der folgenden Gruppen in Frage:
- (1) Anlagerungsprodukte von 2 bis 30 Mol Ethylenoxid und/ oder 0 bis 5 Mol Propylenoxid an lineare Fettalkohole mit 8 bis 22 C-Atomen, an Fettsäuren mit 12 bis 22 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe;
- (2) Glycerinmono- und -diester und Sorbitanmono- und -diester von gesättigten und ungesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen und deren Ethylenoxidanlagerungsprodukte;
- (3) Alkylmono- und -oligoglycoside mit 8 bis 22 Kohlenstoffatomen im Alkylrest und deren ethoxylierte Analoga;
- (4) Polyol- und insbesondere Polyglycerinester wie z.B. Polyglycerinpolyricinoleat oder Polyglyce-rinpoly-12-hydroxystearat. Ebenfalls geeignet sind Gemische von Verbindungen aus mehreren dieser Substanzklassen;
- (5) Partialester auf Basis linearer, verzweigter, ungesättigter bzw. gesättigter C6/22-Fettsäuren, Ricinolsäure sowie 12-Hydroxystearinsäure und Glycerin, Polyglycerin, Pentaerythrit, Dipenta-erythrit, Zuckeralkohole (z.B. Sorbit), Alkylglucoside (z.B. Methylglucosid, Butylglucosid, Lauryl-glucosid) sowie Polyglucoside (z.B. Cellulose);
- (6) Trialkylphosphate sowie Mono-, Di- und/oder Tri-PEG-alkylphosphate;
- (7) Wollwachsalkohole;
- (8) Polysiloxan-Polyalkyl-Polyether-Copolymere bzw. entsprechende Derivate;
- (9) Mischester aus Pentaerythrit, Fettsäuren, Citronensäure und Fettalkohol gemäß
DE-PS 1165574 - (13) Polyalkylenglycole.
- (1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;
- (2) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;
- (3) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs;
- (4) polyol and especially polyglycerol esters such as Polyglycerinpolyricinoleat or Polyglyce-rinpoly-12-hydroxystearat. Also suitable are mixtures of compounds of several of these classes of substances;
- (5) partial esters based on linear, branched, unsaturated or saturated C 6/22 fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, Lauryl glucoside) as well as polyglucosides (eg cellulose);
- (6) trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates;
- (7) wool wax alcohols;
- (8) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;
- (9) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to
DE-PS 1165574 - (13) Polyalkylene glycols.
Die Anlagerungsprodukte von Ethylenoxid und/oder von Propylenoxid an Fettalkohole, Fettsäuren, Alkylphenole, Glycerinmono- und -diester sowie Sorbitanmono- und -diester von Fettsäuren oder an Ricinusöl stellen bekannte, im Handel erhältliche Produkte dar. Es handelt sich dabei um Homologen-gemische, deren mittlerer Alkoxylierungsgrad dem Verhältnis der Stoffmengen von Ethylenoxid und/ oder Propylenoxid und Substrat, mit denen die Anlagerungsreaktion durchgeführt wird, entspricht.The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
C8/18-Alkylmono- und -oligoglycoside, ihre Herstellung und ihre Verwendung als oberflächenaktive Stoffe sind beispielsweise aus
Weiterhin können als Emulgatoren zwitterionische Tenside verwendet werden. Als zwitterionische Tenside werden solche oberflächenaktiven Verbindungen bezeichnet, die im Molekül mindestens eine quartäre Ammoniumgruppe und mindestens eine Carboxylat- und eine Sulfonatgruppe tragen. Besonders geeignete zwitterionische Tenside sind die sogenannten Betaine wie die N-Alkyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosalkyldimethylam-moniumglycinat, N-Acylamino-propyl-N,N-dimethylammoniumglycinate, beispielsweise das Kokosacylaminopropyldimethylammonium-glycinat, und 2-Alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline mit jeweils 8 bis 18 C-Atomen in der Alkyl- oder Acylgruppe sowie das Kokosacylaminoethylhydroxyethylcarboxymethylglycinat, Besonders bevorzugt ist das unter der CTFA-Bezeichnung Cocamidopropyl Betaine bekannte Fettsäureamid-Derivat. Ebenfalls geeignete Emulgatoren sind ampholytische Tenside. Unter ampholytischen Tensiden werden solche oberflächenaktiven Verbindungen verstanden, die außer einer C8/18-Alkyl- oder-Acylgruppe im Molekül mindestens eine freie Aminogruppe und mindestens eine-COOH- oder -SO3H-Gruppe enthalten und zur Ausbildung innerer Salze befähigt sind. Beispiele für geeignete ampho-lytische Tenside sind N-Alkylglycine, N-Alkylpropionsäuren, N-Alkylaminobuttersäuren, N-Alkyliminodipropionsäuren, N-Hydroxyethyl-N-alkylamidopropylglycine, N-Alkyltaurine, N-Alkylsarcosine, 2-Alkylaminopropionsäuren und Alkylaminoessigsäuren mit jeweils etwa 8 bis 18 C-Atomen in der Alkyl-gruppe. Besonders bevorzugte ampholytische Tenside sind das N-Kokosalkylaminopropionat, das Kokosacylaminoethylaminopropionat und das C12/18-Acylsarcosin. Neben den ampholytischen kommen auch quartäre Emulgatoren in Betracht, wobei solche vom Typ der Esterquats, vorzugsweise methyl-quaternierte Difettsäuretriethanolaminester-Salze, besonders bevorzugt sind.Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are those surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammoniumglycinate, for example Kokosalkyldimethylam-moniumglycinat, N-acylamino-propyl-N, N-dimethylammoniumglycinate, for example cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3 carboxymethyl-3-hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particular preference is given to the fatty acid amide derivative known by the CTFA name cocamidopropylbetaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which, apart from a C 8/18 alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO 3 H group and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12/18 acylsarcosine. In addition to the ampholytic, quaternary emulsifiers are also suitable, those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
Als weitere Zusatzsoffe können Substanzen wie beispielsweise Lanolin und Lecithin sowie polyethoxylierte oder acylierte Lanolin- und Lecithinderivate, Polyolfettsäureester, Monoglyceride und Fettsäurealkanolamide verwendet werden, wobei die letzteren gleichzeitig als Schaumstabilisatoren dienen. Bei Bedarf kommen als Konsistenzgeber in erster Linie Fettalkohole mit 12 bis 22 und vorzugsweise 16 bis 18 Kohlenstoffatomen und daneben Partialglyceride in Betracht. Bevorzugt ist eine Kombination dieser Stoffe mit Alkyloligoglucosiden und/oder Fettsäure-N-methylglucamiden gleicher Kettenlänge und/oder Polyglycerinpoly-12-hydroxystearaten. Bei Bedarf sind geeignete Verdickungsmittel beispielsweise Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxy-methylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -di-ester von Fettsäuren, Polyacrylate, (z.B. Carbopole® von Goodrich oder Synthalene® von Sigma), Polyacrylamide, Polyvinylalkohol und Polyvinylpyrrolidon, Tenside wie beispielsweise ethoxylierte Fettsäureglyceride, Ester von Fettsäuren mit Polyolen wie beispielsweise Pentaerythrit oder Trimethy-Iolpropan, Fettalkoholethoxylate mit eingeengter Homologenverteilung oder Alkyloligoglucoside sowie Elektrolyte wie Kochsalz und Ammoniumchlorid.
Je nachdem, welche Eigenschaften die erfindungsgemäß zu verwendende O/W-Emulsion haben soll, können auch geeignete kationische Polymere zugesetzt werden. Diese sind beispielsweise ausgewählt aus kationischen Cellulosederivate, wie z.B. ein quaternierte Hydroxyethylcellulose, die unter der Bezeichnung Polymer JR 400® von Amerchol erhältlich ist, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrrolidon/Vinylimidazol-Polymere wie z.B. Luviquat® (BASF), Kondensationsprodukte von Polyglycolen und Aminen, quaternierte Kollagenpolypeptide wie beispielsweise Lauryldimonium hydroxy-propyl hydrolyzed collagen (Lamequat®L/Grünau), quaternierte Weizenpolypeptide, Polyethylenimin, kationische Siliconpolymere wie z.B. Amidomethicone, Copolymere der Adipinsäure und Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine®/Sandoz), Copolymere der Acrylsäure mit Dime-thyldiallylammoniumchlorid (Merquat® 550/Chemviron), Polyaminopolyamide wie z.B. beschrieben in der
Depending on which properties the O / W emulsion to be used according to the invention is to have, it is also possible to add suitable cationic polymers . These are, for example, selected from cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF), Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimony hydroxy-propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amidomethicones, copolymers of adipic acid and Dimethylaminohydroxypropyldiethylentrimamin (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyl-diallyl ammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides as described, for example, in US Pat
Zur Verbesserung des Fließverhaltens der erfindungsgemäß zu verwendenden O/W-Emulsion können ferner Hydrotrope wie beispielsweise Ethanol, Isopropylalkohol, oder Polyole eingesetzt werden. Polyole, die hier in Betracht kommen, besitzen vorzugsweise 2 bis 15 Kohlenstoffatome und mindestens zwei Hydroxylgruppen. Typische Beispiele sind
- Glycerin;
- Alkylenglycole wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
- technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
- Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
- Niedrigalkylglucoside, insbesondere solche, mit 1 bis 8 Kohlenstoffen im Alkylrest wie beispiels-weise Methyl- und Butylglucosid;
- Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Sorbit oder Mannit,
- Zucker mit 5 bis 12 Kohlenstoffatomen wie beispielsweise Glucose oder Saccharose;
- Aminozucker wie beispielsweise Glucamin.
- glycerol;
- Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
- technical oligoglycerine blends having an inherent degree of condensation of from 1.5 to 10 such as technical grade diglycerin blends having a diglycerol content of from 40 to 50 weight percent;
- Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
- Niedrigalkylglucoside, in particular those having 1 to 8 carbons in the alkyl radical such as, for example, methyl and Butylglucosid;
- Sugar alcohols containing 5 to 12 carbon atoms, such as sorbitol or mannitol,
- Sugars having 5 to 12 carbon atoms such as glucose or sucrose;
- Amino sugars such as glucamine.
In einer bevorzugt Ausführungsform der vorliegenden Erfindung setzt man O/W Emulsionen, enthaltend
- (x) 1 bis 50 Gew.-% Wachsester,
- (a) 0,04 bis 10 Gew.-% Triglyceride,
- (b) 0,04 bis 10 Gew.-% Partialglyceride und
- (c) 0,04 bis 20 Gew.-% Fettalkoholpolyglycolether
- (x) 1 to 50% by weight of wax ester,
- (a) 0.04 to 10% by weight of triglycerides,
- (b) 0.04 to 10% by weight of partial glycerides and
- (c) 0.04 to 20% by weight of fatty alcohol polyglycol ether
Vorzugsweise liegt in den erfindungsgemäß zu verwendenden O/W-Emulsionen zumindestens eine alkoholische Komponente ausgewählt aus Monohydroxy-, Dihydroxy- und Trihydroxy-Verbindungen, in Kombination mit mindestens einer weiteren Komponente ausgewählt aus
stickstoffhaltigen, aliphatischen, organischen Verbindungen mit weniger als 10 C-Atomen im Molekül, vorzugsweise weniger als 7 C-Atomen im Molekül, das besonders bevorzugt eine zusätzliche OH-Gruppe enthält, und/oder
d) einer organischen Carbonsäure mit 1 bis 10 C-Atomen im Molekül, vorzugsweise Essigsäure und/oder Capronsäure vor.Preferably, in the O / W emulsions to be used according to the invention, at least one alcoholic component selected from monohydroxy, dihydroxy and trihydroxy compounds is selected in combination with at least one further component
nitrogen-containing, aliphatic, organic compounds having less than 10 C atoms in the molecule, preferably less than 7 C atoms in the molecule, which particularly preferably contains an additional OH group, and / or
d) an organic carboxylic acid having 1 to 10 carbon atoms in the molecule, preferably acetic acid and / or caproic acid.
Außerdem ist es bevorzugt, dass der Anteil der genannten alkoholischen Komponente, bezogen auf die gesamte erfindungsgemäß zu verwendende Q/W-Emulsion größer als 20 Gew.-%, besonders bevorzugt größer als 50 Gew.-%, jedoch nicht größer als 61,8 Gew.-% ist.In addition, it is preferred that the proportion of said alcoholic component, based on the total Q / W emulsion to be used according to the invention, is greater than 20% by weight, particularly preferably greater than 50% by weight, but not greater than 61.8 Wt .-% is.
Vorzugsweise ist die genannte in der erfindungsgemäß zu verwendende O/W-Emulsion einzusetzende alkoholische Komponente im wesentlichen Glycerin.Preferably, said alcoholic component to be used in the O / W emulsion to be used in the present invention is substantially glycerol.
Als bevorzugt wird weiterhin eine erfindungsgemäß zu verwendende O/W-Emulsion angesehen, in der als genannte stickstoffhaltige Verbindung (d) eine Verbindung der Formel (5)
Für den Fall, dass in der erfindungsgemäß zu verwendenden O/W-Emulsion die genannte stickstoffhaltige Verbindung (d) vorliegt, beträgt ihr Anteil, bezogen auf das gesamte Konzentrat, 0,1 bis 20 Gew.-%.In the case where the nitrogen-containing compound (d) is present in the O / W emulsion to be used according to the invention, its proportion, based on the total concentrate, is 0.1 to 20% by weight.
Für den Fall, dass in der erfindungsgemäß zu verwendenden O/W-Emulsion die genannte organischen Carbonsäure (e), vorliegt, beträgt ihr Anteil, bezogen auf das gesamte Konzentrat, 0,1 bis 20 Gew.-%.In the event that in the present invention to be used O / W emulsion said organic carboxylic acid (s), is present, their proportion, based on the total concentrate, 0.1 to 20 wt .-%.
Es ist weiterhin bevorzugt, dass der Anteil der wässrigen Phase in der erfindungsgemäß zu verwendenden O/W-Emulsion größer als 95 Gew.%, bezogen auf die gesamte O/W-Emulsion, ist. Als wässrige Phase im Sinne der vorliegenden Erfindung sind wenigstens 10 Gew.-% Wasser zusammen mit allen darin enthaltenen Komponenten zu verstehen, mit der Maßgabe, dass sie zusammen eine einzige Phase, ohne Phasengrenzen, darstellen.It is further preferred that the proportion of the aqueous phase in the O / W emulsion to be used according to the invention is greater than 95% by weight, based on the total O / W emulsion. As aqueous phase in the sense of the available invention are at least 10 Gew. -% water together with all contained therein Understand components with the proviso that together they represent a single phase, without phase boundaries.
In einer anderen erfindungsgemäß zu verwendenden O/W-Emulsion liegt diese als Hochkonzentrat vor, das
- (x) 25 bis 50 Gew.-% Wachsester,
- (a) 1 bis 10 Gew.-% Triglyceride,
- (b) 1 bis 10 Gew.-% Partialglyceride und
- (c) 1 bis 20 Gew.-% Fettalkoholpolyglycolether
- (x) 25 to 50% by weight wax ester,
- (a) 1 to 10% by weight of triglycerides,
- (b) 1 to 10% by weight of partial glycerides and
- (c) 1 to 20% by weight of fatty alcohol polyglycol ether
Je nach Formulierung ist es weiterhin bevorzugt, dass die erfindungsgemäß zu verwendende O/W-Emulsion zusätzlich mindestens eine antimikrobielle Komponente ausgewählt aus den Gruppen der Alkohole, Aldehyde, antimikrobiellen Säuren, Carbonsäureester, Säureamide, Phenole, Phenolderivate, Diphenyle, Diphenylalkane, Harnstoffderivate, Sauerstoff-, Stickstoff-Acetale sowie -Formale, Benzamidine, Isothiazoline, Phthalimidderivate, Pyridinderivate, antimikrobiellen oberflächenaktiven Verbindungen, Guanidine, antimikrobiellen amphoteren Verbindungen, Chinoline, 1,2-Dibrom-2,4-dicyanobutan, Iodo-2-propynyl-butyl-carbamat, Iod, Iodophore, Peroxide, Persäuren enthält, wobei die genannten Komponenten unterschiedlich von den bisher genannten in der erfindungsgemäß zu verwendenden O/W-Emulsion enthaltenen Komponenten sind.Depending on the formulation, it is further preferred that the O / W emulsion to be used according to the invention additionally comprises at least one antimicrobial component selected from the groups of the alcohols, aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen , Nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate , Iodine, iodophores, peroxides, peracids, wherein the components mentioned are different from the previously mentioned components contained in the O / W emulsion to be used according to the invention.
Außerdem wird in einer bevorzugten Ausführungsform die erfindungsgemäß zu verwendende O/W-Emulsion unmittelbar vor dem Aufbringen auf die Bänder der genannten Transportbandanlage erzeugt, wobei es besonders bevorzugt ist, wenn die Herstellung der genannten O/W-Emulsion in speziellen für die Herstellung von O/W-Emulsionen geeigneten Mischdüsen erfolgt.In addition, in a preferred embodiment, the O / W emulsion to be used according to the invention is produced immediately prior to application to the belts of said conveyor belt system, it being particularly preferred if the preparation of said O / W emulsion in particular for the production of O / W emulsions suitable mixing nozzles takes place.
Vorzugsweise wird die erfindungsgemäß zu verwendende O/W-Emulsion oder deren verdünnte Lösung zum Transport von Kunststoff-, Karton-, Metall- oder Glas-Gebinden eingesetzt, wobei im Falle von Kunststoff-Gebinden diese besonders bevorzugt mindestens ein Polymer ausgewählt aus den Gruppen der Polyethylenterephthalate (PET), Polyethylennaphtenate (PEN), Polycarbonate (PC), PVC enthalten und ganz besonders bevorzugt PET-Getränke-Flaschen sind.Preferably, the invention to be used O / W emulsion or its dilute solution for the transport of plastic, cardboard, metal or Glass containers used in the case of plastic containers, these more preferably at least one polymer selected from the groups of polyethylene terephthalates (PET), polyethylene naphthenates (PEN), polycarbonates (PC), PVC and very particularly preferably PET beverage bottles are ,
Weiterhin ist es bei der Verwendung der erfindungsgemäß zu verwendenden O/W-Emulsion bevorzugt, dass bei der Anwendung separat zusätzliche antimikrobielle Wirkstoffe, insbesondere organische Persäuren, Chlordioxid oder Ozon, verwendet werden.Furthermore, when using the O / W emulsion to be used according to the invention, it is preferred that separately additional antimicrobial agents, in particular organic peracids, chlorine dioxide or ozone, be used in the application.
Bei der Applikation der erfindungsgemäß zu verwendenden O/W-Emulsion ist es weiterhin bevorzugt, die O/W-Emulsion direkt, ohne vorheriges Verdünnen über eine Applikationsvorrichtung auf die Bänder der Transportanlage aufzubringen.In the application of the O / W emulsion to be used according to the invention, it is further preferred to apply the O / W emulsion directly without prior dilution via an application device to the belts of the transport system.
Ebenso ist es bei der Applikation der erfindungsgemäß zu verwendenden O/W-Emulsion bevorzugt, die O/W-Emulsion in der Transportanlage mit Wasser zu verdünnen, besonders bevorzugt um einen Verdünnungsfaktor, der zwischen 20.000 und 100 liegt, bevor sie über eine Applikationsvorrichtung auf die Bänder der Transportanlage aufgebracht wird.Likewise, in the application of the O / W emulsion to be used according to the invention, it is preferred to dilute the O / W emulsion in the transport system with water, more preferably by a dilution factor of between 20,000 and 100, before it has an application device the belts of the transport system is applied.
In einer anderen bevorzugten Ausführungsform der Applikation der erfindungsgemäß zu verwendenden O/W-Emufsion ist es bevorzugt, dass die Applikationsvorrichtung während der Applikation in direktem Kontakt mit den zu schmierenden Oberflächen steht. Im Sinne der vorliegenden Erfindung ist dabei zu verstehen, dass die Applikation beispielsweise über Pinsel, Schwamm, Lappen, Wischer, die in direktem Kontakt mit der Kette stehen, erfolgt.In another preferred embodiment of the application of the O / W emulsion to be used according to the invention, it is preferred for the application device to be in direct contact with the surfaces to be lubricated during application. For the purposes of the present invention is to be understood that the application, for example via brush, sponge, cloth, wiper, which are in direct contact with the chain occurs.
Je nach Bedarf kann es auch bevorzugt sein, als Applikationsvorrichtung eine Sprühvorrichtung zu verwenden.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein als O/W-Emulsion vorliegendes Schmiermittelkonzentrat enthaltend einen Wachsester, zur Schmierung von Transportbandanlagen in Lebensmittelbetrieben.Depending on requirements, it may also be preferable to use a spraying device as the application device.
Another object of the present invention is a present as O / W emulsion lubricant concentrate containing a wax ester, for the lubrication of conveyor belts in food processing plants.
Vorzugsweise enthält das erfindungsgemäße Schmiermittelkonzentrat mindestens eine weitere Komponente ausgewählt aus den Gruppen der
- a) Triglyceride,
- b) Partialglyceride, oder
- c) Fettalkoholpolyglykolether.
- a) triglycerides,
- b) partial glycerides, or
- c) fatty alcohol polyglycol ether.
Alle Ausführungen, die im Rahmen der Beschreibung der erfindungsgemäß zu verwendenden O/W-Emulsion gemacht wurden gelten analog auch für die erfindungsgemäßen Schmiermittelkonzentrate.All embodiments which were made within the scope of the description of the O / W emulsion to be used according to the invention also apply analogously to the lubricant concentrates according to the invention.
Kettengleitmittelkonzentrate wurden als O/W-Emulsion in unterschiedlicher Zusammensetzung formuliert und auf ihre Eigenschaften hin untersucht. Die Viskosität der Zubereitungen E1 und E2 wurde nach der Brookfield-Methode in einem RVF-Viskosimeter (Spindel 1, 10 Umdrehungen pro Minute (Upm)) einmal unmittelbar nach der Herstellung (20°C) und ein weiteres Mal nach einer Lagerzeit von 4 Wochen bei 45°C gemessen. Die Stabilität der Formulierungen wurde nach Lagerung (4 w, 45°C) optisch bestimmt. Dabei bedeutet "+" stabil und "-" Phasentrennung.
Es wurden Schmierversuche mit den Rezepturen E1 und E3, sowie E4 durchgeführt. Hierfür wurde das Produkt mit Wasser unterschiedlicher Qualität verdünnt, um eine Abhängigkeit des Schmierverhaltens von der Wasserqualität festzustellen. Als Transportgebinde wurden PET-Flaschen in Schmierversuchen auf Versuchstransporteuren getestet. Die Versuche wurden auf die gemäß dem Stand der Technik beschriebene Art und Weise durchgeführt.Lubricating tests were carried out with the formulations E1 and E3, as well as E4. For this purpose, the product was diluted with water of different quality in order to determine a dependence of the lubricating behavior on the water quality. As transport containers, PET bottles were tested in lubricant tests on test transporters. The experiments were carried out in the manner described in the prior art.
Weiterhin wurden die PET-Flaschen auf unterschiedlichen Kettenmaterialien getestet.Furthermore, the PET bottles were tested on different chain materials.
Wie die folgende Tabelle 2 zeigt, wurden sehr gute Schmierwerte erzielt.As the following Table 2 shows, very good lubrication values were achieved.
Die Formulierung E1 weist insbesondere bei salzhaltigem, hartem Wasser hervorragende Schmierwerte auf. Die Formulierungen E3 und E4 zeigen auch bei vollentsalztem Wasser sehr gute Werte.The formulation E1 has excellent lubricating properties, especially with saline, hard water. The formulations E3 and E4 show very good values even in demineralized water.
Ähnliche Eigenschaften wurden in Versuchen auch mit den anderen Formulierungen E2 sowie E5 bis E9 erreicht.
Unter anderem ist bei der Auswertung dieser Versuchsserie hervorzuheben, daß Kombinationen mit Alkoxypropylamin trotz geringerer Wirkstoff-Menge an CetylPalmitat in der Kombination hervorragende Schmierwerte hervorbringen. Dabei ergibt sich als weiterer Vorteil bei derartigen Kombinationen, daß Alkoxypropylenamine zusätzliche antimikrobielle Wirksamkeit zur Kombination beisteuern.Among other things, it should be emphasized in the evaluation of this series of experiments that combinations with alkoxypropylamine produce excellent lubricating values despite the lower amount of active ingredient in cetyl palmitate in the combination. It is a further advantage of such combinations that alkoxypropyleneamines contribute additional antimicrobial efficacy to the combination.
Diese Vorteile konnten in einigen Versuchen bestätigt werden für die bei Kettengleitmitteln bekannten Alkoxypropylamin-Typen der allgemeinen Formel
R-A-(CH2)k-NH-[(CH2)l-NH]y-H·(H+X-)n (V)
wobei
- R
- ein substituierter oder unsubstituierter, linearer oder verzweigter, gesättigter oder einfach oder mehrfach ungesättigter Alkylrest mit 6 bis 22 C-Atomen, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen und Carboxy, oder
ein substituierter oder unsubstituierter Phenylrest, wobei die Substituenten ausgewählt sind aus Amino, Imino, Hydroxy, Halogen, Carboxy und einem linearen oder verzweigten, gesättigten oder einfach oder mehrfach ungesättigten Alkylrest mit 6 bis 22 C-Atomen, ist; - A
- für -O- steht,
- X-
- ein Anion einer anorganischen oder organischen Säure bedeutet,
- k, l
- unabhängig voneinander eine ganze Zahl im Bereich von 1 bis 6 ist;
- y
- O, 1, 2, 3, 4 oder 5 ist,
- n
- eine ganze Zahl von 0 bis 6 ist.
RA- (CH 2) k -NH - [(CH 2) l -NH] y -H · (H + X -) n (V)
in which
- R
- a substituted or unsubstituted, linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 C atoms, wherein the substituents are selected from amino, imino, hydroxy, halogen and carboxy, or
a substituted or unsubstituted phenyl radical wherein the substituents are selected from amino, imino, hydroxy, halogen, carboxy and a linear or branched, saturated or mono- or polyunsaturated alkyl radical having 6 to 22 carbon atoms; - A
- stands for -O-,
- X -
- an anion of an inorganic or organic acid means
- k, l
- independently is an integer in the range of 1 to 6;
- y
- O, 1, 2, 3, 4 or 5,
- n
- is an integer from 0 to 6.
Im übrigen wurden auch sehr gute Schmierwerte durch Kombination der erfindungsgemäßen Schmiermittelkonzentrate mit Aminen der Formel (V) erzielt, in denen A einer -NH-Gruppe entsprach.Incidentally, very good lubrication values were also achieved by combining the lubricant concentrates according to the invention with amines of the formula (V) in which A corresponded to an -NH group.
Darüberhinaus gelangt man zu guten Ergebnissen, wenn man die erfindungsgemäßen Schmiermittelkonzentrate mit den aus Literatur und Praxis bekannten Kettengleitmittel-Wirkstoffen gemäß den Formeln (I), (II)a, (IIb), (IIIa), (IIIb), (IIIc), (IVa) und/oder (IVb) kombiniert.Moreover, good results are obtained when the lubricant concentrates according to the invention with known from literature and practice chain lubricant agents according to the formulas (I), (II) a, (IIb), (IIIa), (IIIb), (IIIc), (IVa) and / or (IVb) combined.
Bei derartigen Kombinationen gelingt es, die ansonsten erforderliche Wirkstoffkonzentration von, aufgrund toxikologischer und ökologischer Bedenken, oft kritisch gesehenen Aminen nach Belieben zu reduzieren.With such combinations, it is possible to reduce the otherwise required active ingredient concentration of, due to toxicological and ecological concerns, often critical seen amines at will.
Dementsprechend bereichert die vorliegende Erfindung auch die Auswahl der Formulierungs-Resourcen für den Anwendungstechniker.Accordingly, the present invention also enriches the selection of formulation resources for the application engineer.
Die mit aminhaltigen Kettengleitmittel-Wirkstoffen kombinierten SchmiermittelKonzentrate sind in der Regel ausreichend gut antimikrobiell wirksam, um in der Praxis Keimwachstum zu verhindern oder sogar Keime abzutöten. Fehlen diese Kombinationswirkstoffe oder ist ihre Konzentration nicht hoch genug, so können bei Bedarf selbstverständlich weitere antimikrobielle Wirkstoffe zugegeben werden.The lubricant concentrates combined with amine-containing chain lubricant agents are generally sufficiently effective antimicrobial to prevent in practice germ growth or even kill germs. If these combination active ingredients are lacking or if their concentration is not high enough, further antimicrobial active ingredients can of course be added if required.
Dies ist nur beispielhaft in den Beispielen E6, E7, E8 und E9 vorgemacht. Daneben gibt es viele weitere Möglichkeiten.This is only exemplified in Examples E6, E7, E8 and E9. There are many other possibilities as well.
Zur Bestimmung der Materialverträglichkeit wurde die TNO-Methode herangezogen. Dazu wurde die Rezeptur E1 ohne Verdünnung und als Anwendungslösung mit 1% eingesetzt.To determine the material compatibility, the TNO method was used. For this purpose, the formulation E1 was used without dilution and as an application solution with 1%.
Laut Versuchsbeschreibung werden PET-Flaschen mit Wasser gefüllt und mit Kohlendioxid so konditioniert, dass im Innenbereich der Flaschen ein Druck von etwa 7 bar vorliegt. Danach werden die Bodentassen der Flaschen in die Formulierung des Vergleichsbeispiels bzw. des erfindungsgemäß zu vewendenden Beispiels getaucht und über einen Zeitraum von 24 Stunden in eine Petri-Schale gestellt. Nach den 24 Stunden werden die Flaschen geöffnet, entleert und die Bodentassen mit Wasser abgespült. Bei visueller Auswertung der Bodentassen kann man feststellen, dass bei dem Versuch mit dem erfindungsgemäß zu verwendenden Beispiel festzustellen ist, dass im Bodenbereich nur wenige Spannungsrisse mit geringer Tiefe, Einstufung A, vorliegen. Die Einstufung erfolgt in Anlehnung an die Referenzbilder, die in Kapitel IV-22 des Buches
Demzufolge ist das Verhalten gegenüber PET-Flaschen ebenfalls positiv zu bewerten: Für beide Versuche wurde geringe Spannungsrisskorrosion nur in der Bodentasse festgestellt. Der Standring wies keine Spannungsrisskorrosion auf.Consequently, the behavior towards PET bottles is also to be evaluated positively: For both tests, low stress corrosion cracking was only detected in the bottom cup. The base ring showed no stress corrosion cracking.
Es wurde, wie bereits dargestellt, festgestellt, dass die Persistenz der Anwendungslösung des erfindungsgemäßen Mittels E1 auf den Ketten mit steigender Wasserhärte zunimmt.It was, as already stated, found that the persistence of the application solution of the inventive composition E1 increases on the chains with increasing water hardness.
Demzufolge kann durch Erhöhung der Wasserhärte auch eine Verlängerung der Pausen zwischen den Dosierzeiten erreicht werden.Consequently, by increasing the water hardness, an extension of the pauses between the metering times can be achieved.
Claims (4)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10146264A DE10146264A1 (en) | 2001-09-20 | 2001-09-20 | Use of O / W emulsions for chain lubrication |
EP02799361.7A EP1427801B8 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
PCT/EP2002/010157 WO2003027217A1 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
Related Parent Applications (2)
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EP02799361.7A Division-Into EP1427801B8 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
EP02799361.7A Division EP1427801B8 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
Publications (1)
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EP3508563A1 true EP3508563A1 (en) | 2019-07-10 |
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EP02799361.7A Expired - Lifetime EP1427801B8 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
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EP02799361.7A Expired - Lifetime EP1427801B8 (en) | 2001-09-20 | 2002-09-11 | Use of o/w emulsions for chain lubrication |
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US (5) | US7297666B2 (en) |
EP (2) | EP3508563A1 (en) |
DE (1) | DE10146264A1 (en) |
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WO (1) | WO2003027217A1 (en) |
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Also Published As
Publication number | Publication date |
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EP1427801B8 (en) | 2019-04-24 |
US7297666B2 (en) | 2007-11-20 |
US10400190B2 (en) | 2019-09-03 |
US8759263B2 (en) | 2014-06-24 |
US9249370B2 (en) | 2016-02-02 |
WO2003027217A1 (en) | 2003-04-03 |
EP1427801B1 (en) | 2019-03-20 |
EP1427801A1 (en) | 2004-06-16 |
US9758742B2 (en) | 2017-09-12 |
US20170335219A1 (en) | 2017-11-23 |
PL369523A1 (en) | 2005-05-02 |
US20160108334A1 (en) | 2016-04-21 |
US20050070448A1 (en) | 2005-03-31 |
US20140336091A1 (en) | 2014-11-13 |
US20080108532A1 (en) | 2008-05-08 |
DE10146264A1 (en) | 2003-04-17 |
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