EP0848746B1 - Aqueous cleaning agent - Google Patents
Aqueous cleaning agent Download PDFInfo
- Publication number
- EP0848746B1 EP0848746B1 EP96920820A EP96920820A EP0848746B1 EP 0848746 B1 EP0848746 B1 EP 0848746B1 EP 96920820 A EP96920820 A EP 96920820A EP 96920820 A EP96920820 A EP 96920820A EP 0848746 B1 EP0848746 B1 EP 0848746B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- cleaner
- weight
- alcohol
- alkoxylation
- 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.)
- Revoked
Links
- 239000012459 cleaning agent Substances 0.000 title abstract description 17
- 239000004435 Oxo alcohol Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims 1
- 235000019832 sodium triphosphate Nutrition 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000001226 triphosphate Substances 0.000 claims 1
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 24
- 239000002562 thickening agent Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003599 detergent Substances 0.000 description 7
- -1 alkyl ether sulfates Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 1
- IKYKEVDKGZYRMQ-PDBXOOCHSA-N (9Z,12Z,15Z)-octadecatrien-1-ol Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCO IKYKEVDKGZYRMQ-PDBXOOCHSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- ALSTYHKOOCGGFT-MDZDMXLPSA-N oleyl alcohol Chemical compound CCCCCCCC\C=C\CCCCCCCCO ALSTYHKOOCGGFT-MDZDMXLPSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to an aqueous cleaning agent, the nonionic Contains surfactants and is suitable for cleaning in the sanitary area.
- the pH value of acidic cleaning agents is usually between 0 and 2. Such a low pH value makes the stability of the components special Conditions.
- the thickeners used to increase the viscosity e.g. Amines, or amine derivatives, often supply products that are not are stable in viscosity over a sufficient period of time. On top of that at these thickeners the viscosity of the products strongly depending on the storage temperature can fluctuate.
- Other typical thickeners like guar flour, Xanthan gum or cellulose derivatives are not stable and in acidic media quickly lose their thickening properties. Another disadvantage of this Connections is that they do not contribute to the cleaning performance of the Afford detergents.
- nonionic surfactants especially tertiary Amines, used as thickeners in sanitary cleaners. Your storage stability however, is not sufficient.
- a sanitary cleaning agent is described as Thickeners alkyl ether sulfates, amphoteric surfactants or mixtures of contains nonionic surfactants with ethoxylated amines.
- nonionic surfactants alone high concentrations of surfactants must be used to ensure sufficient thickening to reach.
- EP-A1-0 475 002 discloses a sanitary cleaning agent which consists of 2 to 40% by weight of acid, 2 to 10% by weight of C 10 -C 18 fatty alcohol ethoxylate with 8 to 14 EO units and 2 up to 10% by weight of thickener, in which a C 10 -C 18 fatty alcohol ethoxylate with 1 to 7 EO units is used as the thickener and the free fatty alcohol content is below 5%.
- the examples in this document show that the viscosity decreases sharply when higher fatty alcohol contents are used. It is therefore necessary to use the starting products in high purity, which increases the costs of these products.
- the present invention has for its object aqueous cleaning agents to make available over a long storage period those from the known Products do not have disadvantages and from raw materials usual technical quality and purity can be produced.
- the surfactant mixture from the nonionic Surfactants a, b, and c namely fatty alcohol alkoxylates with different Degree of alkoxylation and oxo alcohol alkoxylates, a thickening effect in detergents.
- Cleaning agents can be obtained Viscosity by dilution e.g. B. with water over a wide, with detergents usual range can be set and that also with the various pH values of these agents is stable over a long period of time.
- the aqueous cleaning agents according to the invention preferably have a viscosity at 20 ° C from 15 s to 90 s, measured in a Ford cup with an opening of 4 mm, measured on what is about a Brookfield viscosity of 20 mPas to 800 mPas with spindle 1. If desired, the viscosity can also be chosen higher up to a gel-like consistency.
- the C 12 -C 22 alcohol alkoxylates which are used as components a) and b) in the agent according to the invention are nonionic surfactants of the formula I. wherein R 1 represents a saturated or unsaturated C 12 -C 22 alkyl group, R 2 represents hydrogen and / or a methyl group and for component a) m for numbers from 6 to 15 and for component b) m for numbers from 2 to 5 stands.
- the compounds can be obtained by alkoxylation of C 12 -C 22 alcohols.
- Suitable C 12 -C 22 alcohols are, for example, the native vegetable-based fatty alcohols such as, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behen alcohol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol and their technical mixtures, such as coconut oil or palm oil, palm alcohol also peanut fatty alcohol.
- mixed alkoxylates ie that m is greater than 1 and R 2 is hydrogen and methyl, up to 4 propylene oxide units, preferably 2 to 4 propylene oxide units, are generally present.
- C 12 -C 18 fatty alcohol ethoxylates are particularly preferably used.
- C 10 -C 15 oxo alcohol alkoxylates ie alkoxylates of branched C 10 -C 15 oxo alcohols, are also known compounds which can be obtained in a known manner by alkoxylation of oxo alcohols.
- the oxo alcohols used are compounds made from petrochemical raw materials, e.g. B. can be obtained by Roeln's oxosynthesis.
- C 13 -C 15 oxo alcohol ethoxylates are particularly preferably used as oxo alcohol alkoxylates.
- each of the three surfactants a, b and c can be used in an amount of 10 up to 80% by weight, preferably 15 to 50% by weight, based on the surfactant mixture.
- the content of this surfactant combination is preferred in the finished cleaner between 2 and 30% by weight, preferably between 5 and 20% by weight, based on the finished detergent.
- the acidic cleaning agents preferred according to the invention contain as further Ingredient acid. All non-corrosive acids are suitable. To be favoured Citric acid, glycolic acid, acetic acid, formic acid, lactic acid, dicarboxylic acids such as. Succinic acid, oxalic acid, adipic acid, phosphoric acid, amidosulfonic acid or mixtures of the acids mentioned.
- the acids are usually contained in an amount between 2 and 40 wt .-%.
- the amount of Acid used depends on the type of acid and the desired pH from which is preferably below 3 and in particular between 0 and 2.
- Cleaning agents according to the invention with an alkaline pH contain, in addition to the surfactants, alkaline salts, such as phosphates, in amounts of preferably up to 10% by weight, in particular 2 to 5% by weight, or free alkalis, such as NH 3 , alkanolamines, KOH or NaOH, in amounts preferably up to 8% by weight, in particular between 0.1 and 2% by weight. Mixtures of several alkalizing agents can of course also be present. The pH of these agents is preferably above 9, in particular between 10 and 14.
- the agent according to the invention can furthermore contain anionic surfactants as cleaning-active components.
- Suitable anionic surfactants are, for example, C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkanesulfonates, C 8 -C 18 ⁇ -olefin sulfonates, sulfonated C 8 -C 18 fatty acid C 1 - C 4 alkyl esters, C 6 -C 18 alkylbenzenesulfonates, sulfosuccinic acid mono- and di-C 8 -C 12 alkyl esters, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-Sarcosinate and C 8 -C 18 alkyl isethionates.
- the anionic surfactants can be used in amounts of up to 10% by weight, preferably 0.1 to 2.0 % By weight, based on the total agent, may be present.
- the cleaning agent according to the invention can contain further optional components contain such active ingredients and auxiliaries in such agents, provided they have the properties do not impair the agents according to the invention, for example dyes in an amount up to 1% by weight, fragrances in an amount up to 2% by weight and corrosion inhibitors in an amount up to 5 wt .-%, each based on the Amount of finished detergent.
- Other ingredients come as well Solvents such as ethanol, isopropanol or glycol ether in an amount of 1 to 20 wt .-% or neutral salts into consideration.
- the cleaning agents of the following examples were made by simple mixing of the components.
- the viscosity of the agents obtained became Brookfield with spindle 1 at 20 ° C and a suitable speed between 10 and 100 Revolutions per minute (rpm) measured. Unless otherwise noted, are the contents are given in percent by weight.
- This example gave a viscosity of 160 mPas.
- Citric acid 4.5% C 16 -C 18 fatty alcohol + 10 EO 3.5% C 12 -C 15 oxo alcohol + 10 EO 4% C 12 -C 14 fatty alcohol + 4 EO 4% Perfume 0.4% colour 0.002% water ad 100%
- This example gave a viscosity of 75 mPas.
- Citric acid 4.5% C 16 -C 18 fatty alcohol + 10 EO 3.5% C 12 -C 15 oxo alcohol + 10 EO 3.5% C 12 -C 14 fatty alcohol + 4 EO 4% Perfume 0.4% colour 0.002% water ad 100%
- This example gave a viscosity of 320 mPas.
- the viscosity was 105 mPas.
- the pH was 6.5.
- the viscosity was 135 mPas.
- the viscosity was 100 mPas.
- the viscosity was 700 mPas.
- the pH was 12.0.
- the surfactant combination used according to the invention has a thickening effect on the detergent. In doing so as a thickener, only compounds are used that also contribute to cleaning performance of funds.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein wäßriges Reinigungsmittel, das nichtionische Tenside enthält und zur Reinigung im Sanitärbereich geeignet ist.The present invention relates to an aqueous cleaning agent, the nonionic Contains surfactants and is suitable for cleaning in the sanitary area.
Bei vielen Reinigungsmitteln, wie z.B. den Sanitär-Reinigern, ist es erwünscht, daß diese viskos sind, um eine längere Einwirkzeit auf nicht-waagerechten Oberflächen zu erreichen. Der pH-Wert saurer Reinigungsmittel liegt üblicherweise zwischen 0 und 2. Ein derart niedriger pH-Wert stellt an die Stabilität der Komponenten besondere Anforderungen. Die zur Erhöhung der Viskosität eingesetzten Verdickungsmittel, z.B. Amine oder Aminderivate, liefern häufig Produkte, die nicht über einen ausreichenden Zeitraum viskositätsstabil sind. Hinzukommt, daß bei diesen Verdickern die Viskosität der Produkte stark in Abhängigkeit von der Lagertemperatur schwanken kann. Andere typische Verdickungsmittel wie Guar-Mehl, Xanthan Gum oder Cellulose-Derivate sind in sauren Medien nicht stabil und verlieren schnell ihre Verdicker-Eigenschaften. Ein weiterer Nachteil dieser Verbindungen ist, daß sie keinen Beitrag zur Reinigungsleistung der Reinigungsmittel leisten.With many cleaning agents, e.g. the sanitary cleaners, it is desirable that these are viscous for a longer exposure time on non-horizontal surfaces to reach. The pH value of acidic cleaning agents is usually between 0 and 2. Such a low pH value makes the stability of the components special Conditions. The thickeners used to increase the viscosity, e.g. Amines, or amine derivatives, often supply products that are not are stable in viscosity over a sufficient period of time. On top of that at these thickeners the viscosity of the products strongly depending on the storage temperature can fluctuate. Other typical thickeners like guar flour, Xanthan gum or cellulose derivatives are not stable and in acidic media quickly lose their thickening properties. Another disadvantage of this Connections is that they do not contribute to the cleaning performance of the Afford detergents.
Die in neutralen und alkalischen Reinigungsmitteln eingesetzten Verdickungsmitteln führen dazu, daß die Reinigungsmittel sich bei einem gegebenenfalls vorgesehenen Verdünnungsvorgang nur schwer in Wasser auflösen. Neben den vorgenannten Verdickungsmitteln ist dieser Nachteil auch bei synthetischen Polymeren zu beobachten.The thickeners used in neutral and alkaline cleaning agents lead to the detergents becoming stuck to an optionally provided one It is difficult to dissolve the dilution process in water. In addition to the aforementioned This disadvantage is also a disadvantage of synthetic polymers in the case of thickeners to observe.
In der DE-OS 23 59 095 werden z.B. nichtionische Tenside, insbesondere tertiäre Amine, als Verdickungsmittel in Sanitär-Reinigern verwendet. Ihre Lagerstabilität ist jedoch nicht ausreichend.In DE-OS 23 59 095 e.g. nonionic surfactants, especially tertiary Amines, used as thickeners in sanitary cleaners. Your storage stability however, is not sufficient.
In der DE-OS 35 42 970 wird ein Sanitär-Reinigungsmittel beschrieben, das als Verdickungsmittel Alkylethersulfate, amphotere Tenside bzw. Mischungen aus nichtionischen Tensiden mit oxethylierten Aminen enthält. In dieser Schrift wird ausgeführt, daß beim Einsatz von nichtionischen Tensiden allein unerwünscht hohe Konzentrationen an Tensiden einzusetzen sind, um eine ausreichende Verdickung zu erreichen.In DE-OS 35 42 970 a sanitary cleaning agent is described as Thickeners alkyl ether sulfates, amphoteric surfactants or mixtures of contains nonionic surfactants with ethoxylated amines. In this writing stated that undesirable when using nonionic surfactants alone high concentrations of surfactants must be used to ensure sufficient thickening to reach.
Aus der EP-A1-0 475 002 ist ein Sanitär-Reinigungsmittel bekannt, das aus 2 bis 40 Gew.-% Säure, 2 bis 10 Gew.-% C10-C18-Fettalkoholethoxylat mit 8 bis 14 EO-Einheiten und 2 bis 10 Gew.-% Verdickungsmittel besteht, worin als Verdickungsmittel ein C10-C18-Fettalkoholethoxylat mit 1 bis 7 EO-Einheiten verwendet wird und der freie Fettalkoholgehalt unter 5 % beträgt. Den Beispielen dieser Druckschrift kann entnommen werden, daß beim Einsatz von höheren Fettalkoholgehalten die Viskosität stark abnimmt. Es ist also erforderlich, die Ausgangsprodukte in hoher Reinheit einzusetzen, was die Kosten dieser Produkte erhöht.EP-A1-0 475 002 discloses a sanitary cleaning agent which consists of 2 to 40% by weight of acid, 2 to 10% by weight of C 10 -C 18 fatty alcohol ethoxylate with 8 to 14 EO units and 2 up to 10% by weight of thickener, in which a C 10 -C 18 fatty alcohol ethoxylate with 1 to 7 EO units is used as the thickener and the free fatty alcohol content is below 5%. The examples in this document show that the viscosity decreases sharply when higher fatty alcohol contents are used. It is therefore necessary to use the starting products in high purity, which increases the costs of these products.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, wäßrige Reinigungsmittel zur Verfügung zu stellen, die über einen langen Lagerzeitraum die aus den bekannten Produkten auftretenden Nachteile nicht aufweisen und aus Rohstoffen üblicher technischer Qualität und Reinheit hergestellt werden können.The present invention has for its object aqueous cleaning agents to make available over a long storage period those from the known Products do not have disadvantages and from raw materials usual technical quality and purity can be produced.
Gegenstand der vorliegenden Erfindung sind wäßrige Reinigungsmittel, die ein
Tensidgemisch aus nichtionischen Tensiden aus
Überraschenderweise wurde festgestellt, daß das Tensidgemisch aus den nichtionischen Tensiden a, b, und c, nämlich Fettalkoholalkoxylate mit unterschiedlichen Alkoxylierungsgraden und Oxoalkoholalkoxylate, eine verdickende Wirkung in Reinigungsmitteln hat. Es können Reinigungsmittel erhalten werden, deren Viskosität durch Verdünnung z. B. mit Wasser über einen weiten, bei Reinigungsmitteln üblichen Bereich eingestellt werden kann und die auch bei den verschiedenen pH-Werten dieser Mittel über einen langen Zeitraum stabil ist. Surprisingly, it was found that the surfactant mixture from the nonionic Surfactants a, b, and c, namely fatty alcohol alkoxylates with different Degree of alkoxylation and oxo alcohol alkoxylates, a thickening effect in detergents. Cleaning agents can be obtained Viscosity by dilution e.g. B. with water over a wide, with detergents usual range can be set and that also with the various pH values of these agents is stable over a long period of time.
Die erfindungsgemäßen wäßrigen Reinigungsmittel weisen vorzugsweise eine Viskosität bei 20°C von 15 s bis 90 s, gemessen im Fordbecher mit einer Öffnung von 4 mm, auf, was etwa einer Brookfield-Viskosität von 20 mPas bis 800 mPas, gemessen mit Spindel 1, entspricht. Gewünschtenfalls kann die Viskosität aber auch höher gewählt werden bis hin zu einer gelförmigen Konsistenz.The aqueous cleaning agents according to the invention preferably have a viscosity at 20 ° C from 15 s to 90 s, measured in a Ford cup with an opening of 4 mm, measured on what is about a Brookfield viscosity of 20 mPas to 800 mPas with spindle 1. If desired, the viscosity can also be chosen higher up to a gel-like consistency.
Die C12-C22 -Alkoholalkoxylate, die als Komponenten a) und b) im erfindungsgemäßen Mittel eingesetzt werden sind nichtionische Tenside der Formel I worin R1 für eine gesättigte oder ungesättigte C12-C22-Alkylgruppe, R2 für Wasserstoff und/oder eine Methylgruppe stehen und für Komponente a) m für Zahlen von 6 bis 15 und für Komponente b) m für Zahlen von 2 bis 5 steht. Die Verbindungen können durch Alkoxylierung von C12-C22 -Alkoholen erhalten werden. Geeignete C12-C22-Alkohole sind beispielsweise die nativen Fettalkohole auf pflanzlicher Basis wie z.B. Laurylalkohol, Myristylalkohol, Cetylalkohol, Stearylalkohol, Behenalkohol, Oleylalkohol, Elaidylalkohol, Ricinolalkohol, Linoleylalkohol, Linolenylalkohol sowie deren technischen Gemische, wie Kokosfettalkohol, Palm- und Palmkernfettalkohol oder auch Erdnussfettalkohol. Für den Fall, daß gemischte Alkoxylate eingesetzt werden, d. h. daß m größer als 1 ist und R2 für Wasserstoff und Methyl steht, sind in der Regel bis zu 4 Propylenoxideinheiten, vorzugsweise 2 bis 4 Propylenoxideinheiten enthalten. Besonders bevorzugt werden C12-C18-Fettalkoholethoxylate eingesetzt.The C 12 -C 22 alcohol alkoxylates which are used as components a) and b) in the agent according to the invention are nonionic surfactants of the formula I. wherein R 1 represents a saturated or unsaturated C 12 -C 22 alkyl group, R 2 represents hydrogen and / or a methyl group and for component a) m for numbers from 6 to 15 and for component b) m for numbers from 2 to 5 stands. The compounds can be obtained by alkoxylation of C 12 -C 22 alcohols. Suitable C 12 -C 22 alcohols are, for example, the native vegetable-based fatty alcohols such as, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behen alcohol, oleyl alcohol, elaidyl alcohol, ricinol alcohol, linoleyl alcohol, linolenyl alcohol and their technical mixtures, such as coconut oil or palm oil, palm alcohol also peanut fatty alcohol. In the event that mixed alkoxylates are used, ie that m is greater than 1 and R 2 is hydrogen and methyl, up to 4 propylene oxide units, preferably 2 to 4 propylene oxide units, are generally present. C 12 -C 18 fatty alcohol ethoxylates are particularly preferably used.
C10-C15-Oxoalkoholalkoxylate, d.h. Alkoxylate von verzweigten C10-C15-Oxoalkoholen, sind ebenfalls bekannte Verbindungen, die in bekannter Weise durch Alkoxylierung von Oxoalkoholen erhalten werden können. Die eingesetzten Oxoalkohole sind Verbindungen, die aus petrochemischen Rohstoffen, z. B. durch die Roeln'schen Oxosynthese, erhalten werden können. Als Oxoalkoholalkoxylate werden besonders bevorzugt C13-C15-Oxoalkoholethoxylate eingesetzt.C 10 -C 15 oxo alcohol alkoxylates, ie alkoxylates of branched C 10 -C 15 oxo alcohols, are also known compounds which can be obtained in a known manner by alkoxylation of oxo alcohols. The oxo alcohols used are compounds made from petrochemical raw materials, e.g. B. can be obtained by Roeln's oxosynthesis. C 13 -C 15 oxo alcohol ethoxylates are particularly preferably used as oxo alcohol alkoxylates.
Im Tensidgemisch kann jedes der drei Tenside a, b und c in einer Menge von 10 bis 80 Gew.-%, bevorzugt 15 bis 50 Gew.-%, bezogen auf das Tensidgemisch, vorliegen. Im fertigen Reiniger liegt der Gehalt dieser Tensidkombination bevorzugt zwischen 2 und 30 Gew.-%, bevorzugt zwischen 5 und 20 Gew.-%, bezogen auf das fertige Reinigungsmittel.In the surfactant mixture, each of the three surfactants a, b and c can be used in an amount of 10 up to 80% by weight, preferably 15 to 50% by weight, based on the surfactant mixture. The content of this surfactant combination is preferred in the finished cleaner between 2 and 30% by weight, preferably between 5 and 20% by weight, based on the finished detergent.
Die erfindungsgemäß bevorzugten sauren Reinigungsmittel enthalten als weiteren Bestandteil Säure. Es eignen sich alle nicht-korrosiven Säuren. Bevorzugt werden Citronensäure, Glykolsäure, Essigsäure, Ameisensäure, Milchsäure, Dicarbonsäuren wie z.B. Bernsteinsäure, Oxalsäure, Adipinsäure, Phosphorsäure, Amidosulfonsäure oder Mischungen der genannten Säuren eingesetzt. Die Säuren sind üblicherweise in einer Menge zwischen 2 und 40 Gew.-% enthalten. Die Menge der eingesetzten Säure hängt von der Art der Säure und dem gewünschten pH-Wert ab, der vorzugsweise unterhalb von 3 und insbesondere zwischen 0 und 2 liegt.The acidic cleaning agents preferred according to the invention contain as further Ingredient acid. All non-corrosive acids are suitable. To be favoured Citric acid, glycolic acid, acetic acid, formic acid, lactic acid, dicarboxylic acids such as. Succinic acid, oxalic acid, adipic acid, phosphoric acid, amidosulfonic acid or mixtures of the acids mentioned. The acids are usually contained in an amount between 2 and 40 wt .-%. The amount of Acid used depends on the type of acid and the desired pH from which is preferably below 3 and in particular between 0 and 2.
Erfindungsgemäße Reinigungsmittel mit alkalischem pH-Wert enthalten neben den Tensiden alkalisch reagierende Salze, wie beispielsweise Phosphate, in Mengen vorzugsweise bis 10 Gew.-%, insbesondere 2 bis 5 Gew.-%, oder freie Alkalien, wie beispielsweise NH3, Alkanolamine, KOH oder NaOH, in Mengen vorzugsweise bis zu 8 Gew.-%, insbesondere zwischen 0,1 und 2 Gew.-%. Selbstverständlich können auch Gemische mehrerer Alkalisierungsmittel enthalten sein. Der pH-Wert dieser Mittel liegt vorzugsweise über 9, insbesondere zwischen 10 und 14.Cleaning agents according to the invention with an alkaline pH contain, in addition to the surfactants, alkaline salts, such as phosphates, in amounts of preferably up to 10% by weight, in particular 2 to 5% by weight, or free alkalis, such as NH 3 , alkanolamines, KOH or NaOH, in amounts preferably up to 8% by weight, in particular between 0.1 and 2% by weight. Mixtures of several alkalizing agents can of course also be present. The pH of these agents is preferably above 9, in particular between 10 and 14.
Als reinigungsaktive Bestandteile kann des erfindungsgemäße Mittel weiterhin anionische Tenside enthalten. Geeignete Aniontenside sind z.B. C8-C18-Alkylsulfate, C8-C18-Alkylethersulfate, C8-C18-Alkansulfonate, C8-C18-α-Olefinsulfonate, sulfonierte C8-C18-Fettsäure-C1-C4-Alkylester, C6-C18-Alkylbenzolsulfonate, Sulfobernsteinsäuremono- und -di-C8-C12-Alkylester, C8-C18-Alkylpolyglykolethercarboxylate, C8-C18-N-Acyltauride, C8-C18-N-Sarcosinate und C8-C18-Alkylisethionate.The agent according to the invention can furthermore contain anionic surfactants as cleaning-active components. Suitable anionic surfactants are, for example, C 8 -C 18 alkyl sulfates, C 8 -C 18 alkyl ether sulfates, C 8 -C 18 alkanesulfonates, C 8 -C 18 α-olefin sulfonates, sulfonated C 8 -C 18 fatty acid C 1 - C 4 alkyl esters, C 6 -C 18 alkylbenzenesulfonates, sulfosuccinic acid mono- and di-C 8 -C 12 alkyl esters, C 8 -C 18 alkyl polyglycol ether carboxylates, C 8 -C 18 -N-acyl taurides, C 8 -C 18 -N-Sarcosinate and C 8 -C 18 alkyl isethionates.
Die Aniontenside können in Mengen bis 10 Gew.-%, vorzugsweise 0,1 bis 2,0 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein.The anionic surfactants can be used in amounts of up to 10% by weight, preferably 0.1 to 2.0 % By weight, based on the total agent, may be present.
Als fakultative Bestandteile kann das erfindungsgemäße Reinigungsmittel weitere in derartigen Mitteln übliche Wirk- und Hilfsstoffe enthalten, sofern sie die Eigenschaften der erfindungsgemäßen Mittel nicht eeinträchtigen, beispielsweise Farbstoffe in einer Menge bis zu 1 Gew.-%, Duftstoffe in einer Menge bis zu 2 Gew.-% und Korrosionsinhibitoren in einer Menge bis zu 5 Gew.-%, jeweils bezogen auf die Menge des fertigen Reinigungsmittels. Als weitere Bestandteile kommen auch Lösungsmittel wie Ethanol, Isopropanol oder Glykolether in einer Menge von 1 bis 20 Gew.-% oder Neutralsalze in Betracht.The cleaning agent according to the invention can contain further optional components contain such active ingredients and auxiliaries in such agents, provided they have the properties do not impair the agents according to the invention, for example dyes in an amount up to 1% by weight, fragrances in an amount up to 2% by weight and corrosion inhibitors in an amount up to 5 wt .-%, each based on the Amount of finished detergent. Other ingredients come as well Solvents such as ethanol, isopropanol or glycol ether in an amount of 1 to 20 wt .-% or neutral salts into consideration.
Die folgenden Beispiele sollen die Erfindung näher erläutern, ohne diese darauf zu beschränken. The following examples are intended to explain the invention in more detail without being directed thereto restrict.
Die Reinigungsmittel der folgenden Beispiele wurden durch einfaches Vermischen der Komponenten hergestellt. Die Viskosität der erhaltenen Mittel wurde nach Brookfield mit Spindel 1 bei 20 °C und geeigneter Drehzahl zwischen 10 und 100 Umdrehungen pro Minute (UpM) gemessen. Soweit nichts anderes vermerkt, sind die Gehalte in Gewichtsprozent angegeben.The cleaning agents of the following examples were made by simple mixing of the components. The viscosity of the agents obtained became Brookfield with spindle 1 at 20 ° C and a suitable speed between 10 and 100 Revolutions per minute (rpm) measured. Unless otherwise noted, are the contents are given in percent by weight.
Dieses Beispiel ergab eine Viskosität von 160 mPas.This example gave a viscosity of 160 mPas.
Dieses Beispiel ergab eine Viskosität von 75 mPas.This example gave a viscosity of 75 mPas.
Dieses Beispiel ergab eine Viskosität von 95 mPas.This example gave a viscosity of 95 mPas.
Dieses Beispiel ergab eine Viskosität von 320 mPas.This example gave a viscosity of 320 mPas.
Die Viskosität lag bei 105 mPas.The viscosity was 105 mPas.
Der pH-Wert betrug 6,5.The pH was 6.5.
Die Viskosität betrug 135 mPas. The viscosity was 135 mPas.
Die Viskosität betrug 100 mPas.The viscosity was 100 mPas.
Die Viskosität betrug 700 mPas.
Der pH-Wert lag bei 12,0.The viscosity was 700 mPas.
The pH was 12.0.
Aus den Beispielen ist ersichtlich, daß die erfindungsgemäß eingesetzte Tensidkombination eine verdickende Wirkung auf das Reingungsmittel hat. Dabei werden als Verdicker nur Verbindungen verwendet, die gleichzeitig zur Reinigungsleistung der Mittel beitragen.From the examples it can be seen that the surfactant combination used according to the invention has a thickening effect on the detergent. In doing so As a thickener, only compounds are used that also contribute to cleaning performance of funds.
Claims (6)
- A water-based cleaner containing 2 to 30% by weight of a surfactant mixture of nonionic surfactants consisting ofa) C12-12 alcohol alkoxylates with a degree of alkoxylation of 6 to 15,b) C12-22 alcohol alkoxylates with a degree of alkoxylation of 2 to 5 andc) C10-15 oxoalcohol alkoxylates with a degree of alkoxylation of 5 to 15.
- A cleaner as claimed in claim 1, characterized in that the surfactant mixture contains 10 to 80% by weight and preferably 15 to 50% by weight of each of surfactants a), b) and c), based on the surfactant mixture.
- A cleaner as claimed in claim 1 or 2, characterized in that surfactants a), b) and c) together are present in a quantity of 5 to 20% by weight, based on the final cleaner.
- A cleaner as claimed in any of claims 1 to 3, characterized in that it has a Brookfield viscosity of 200 to 800 mPas, as measured at 20°C using spindle 1.
- An acidic cleaner as claimed in any of claims 1 to 4, characterized in that it contains citric acid, glycolic acid, acetic acid, formic acid, lactic acid, dicarboxylic acid, phosphoric acid, amidosulfonic acid or mixtures thereof as the acid.
- An alkaline cleaner as claimed in any of claims 1 to 4, characterized in that it contains tetrapotassium pyrophosphate, pentasodium triphosphate, potassium hydroxide, sodium hydroxide, ammonia, alkanolamine or a mixture of substances from this group as its alkaline component.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19523117A DE19523117A1 (en) | 1995-06-26 | 1995-06-26 | Aqueous acidic detergent |
DE19523117 | 1995-06-26 | ||
PCT/EP1996/002595 WO1997001622A1 (en) | 1995-06-26 | 1996-06-17 | Aqueous cleaning agent |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0848746A1 EP0848746A1 (en) | 1998-06-24 |
EP0848746B1 true EP0848746B1 (en) | 1999-12-01 |
Family
ID=7765250
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96920820A Revoked EP0848746B1 (en) | 1995-06-26 | 1996-06-17 | Aqueous cleaning agent |
Country Status (8)
Country | Link |
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EP (1) | EP0848746B1 (en) |
AT (1) | ATE187198T1 (en) |
DE (2) | DE19523117A1 (en) |
DK (1) | DK0848746T3 (en) |
ES (1) | ES2141513T3 (en) |
GR (1) | GR3032067T3 (en) |
PT (1) | PT848746E (en) |
WO (1) | WO1997001622A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19751859A1 (en) * | 1997-11-22 | 1999-07-29 | Henkel Ecolab Gmbh & Co Ohg | Means for cleaning hard surfaces |
EP1149945A1 (en) * | 2000-04-29 | 2001-10-31 | Ciba Spezialitätenchemie Pfersee GmbH | Composition for the pretreatment of fibrous materials |
DE10304929A1 (en) * | 2003-02-06 | 2004-08-26 | Glienke, Peter O. | Lime-scale removing and cleaning composition, e.g. for steam irons or sanitary applications, comprising aqueous glycolic acid solution containing sulfated or hydrogenated, ethoxylated castor oil |
DE10311429A1 (en) * | 2003-03-13 | 2004-09-23 | Thomas Hartl | Combined washing-up agent for crockery and cutlery comprises a combination of a de-fatting and a de-scaling agent stored in a container |
DE102004020017A1 (en) * | 2004-04-21 | 2005-11-17 | Henkel Kgaa | Strongly acidic sanitary cleaner with stabilized viscosity and phase behavior |
DE102005034752A1 (en) * | 2005-07-21 | 2007-01-25 | Henkel Kgaa | Cleaning and care products with improved emulsifying ability |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2529096B2 (en) * | 1975-06-30 | 1979-05-31 | Woellner-Werke, 6700 Ludwigshafen | Agent for cold cleaning of solid surfaces contaminated with grease or grease-like soiling |
GB2011944B (en) * | 1978-01-09 | 1982-06-09 | Unilever Ltd | Liquid detergent composition |
DE3518672A1 (en) * | 1985-05-24 | 1986-11-27 | Basf Ag, 6700 Ludwigshafen | LIQUID CLEANING CONCENTRATE FOR STRONG ALKALINE CLEANING FORMULAS |
US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
DE4028138A1 (en) * | 1990-09-05 | 1992-03-12 | Huels Chemische Werke Ag | VISCOSE ACIDIC DETERGENTS |
DE4029777A1 (en) * | 1990-09-20 | 1992-03-26 | Henkel Kgaa | LIQUID, NON-TENSID COMBINATION WITH IMPROVED CELL TESTABILITY |
EP0598973A1 (en) * | 1992-11-26 | 1994-06-01 | The Procter & Gamble Company | Multi-purpose liquid cleaning composition |
-
1995
- 1995-06-26 DE DE19523117A patent/DE19523117A1/en not_active Withdrawn
-
1996
- 1996-06-17 PT PT96920820T patent/PT848746E/en unknown
- 1996-06-17 DK DK96920820T patent/DK0848746T3/en active
- 1996-06-17 ES ES96920820T patent/ES2141513T3/en not_active Expired - Lifetime
- 1996-06-17 EP EP96920820A patent/EP0848746B1/en not_active Revoked
- 1996-06-17 AT AT96920820T patent/ATE187198T1/en not_active IP Right Cessation
- 1996-06-17 WO PCT/EP1996/002595 patent/WO1997001622A1/en active IP Right Grant
- 1996-06-17 DE DE59603798T patent/DE59603798D1/en not_active Expired - Lifetime
-
1999
- 1999-12-07 GR GR990403156T patent/GR3032067T3/en unknown
Also Published As
Publication number | Publication date |
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ES2141513T3 (en) | 2000-03-16 |
PT848746E (en) | 2000-05-31 |
DE59603798D1 (en) | 2000-01-05 |
EP0848746A1 (en) | 1998-06-24 |
DK0848746T3 (en) | 2000-04-17 |
ATE187198T1 (en) | 1999-12-15 |
GR3032067T3 (en) | 2000-03-31 |
DE19523117A1 (en) | 1997-01-02 |
WO1997001622A1 (en) | 1997-01-16 |
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