EP0693115A1 - Utilisation de concentres liquides pour nettoyer des surfaces dures - Google Patents
Utilisation de concentres liquides pour nettoyer des surfaces duresInfo
- Publication number
- EP0693115A1 EP0693115A1 EP94912548A EP94912548A EP0693115A1 EP 0693115 A1 EP0693115 A1 EP 0693115A1 EP 94912548 A EP94912548 A EP 94912548A EP 94912548 A EP94912548 A EP 94912548A EP 0693115 A1 EP0693115 A1 EP 0693115A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- acid
- cleaning
- surfactants
- agents according
- 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.)
- Ceased
Links
- 235000014666 liquid concentrate Nutrition 0.000 title claims abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 16
- 239000012459 cleaning agent Substances 0.000 claims abstract description 13
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000003021 water soluble solvent Substances 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 19
- -1 alkyl glycosides Chemical class 0.000 claims description 15
- 235000008504 concentrate Nutrition 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229930182470 glycoside Natural products 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 150000002170 ethers Chemical class 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101100436302 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) apg-8 gene Proteins 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000001007 flame atomic emission spectroscopy Methods 0.000 description 3
- 229940050410 gluconate Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 101100110261 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) apg-10 gene Proteins 0.000 description 2
- 101100436336 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) apg-12 gene Proteins 0.000 description 2
- 101100285925 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) apg-14 gene Proteins 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 150000008216 xylosides Chemical class 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BZANQLIRVMZFOS-ZKZCYXTQSA-N (3r,4s,5s,6r)-2-butoxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound CCCCOC1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O BZANQLIRVMZFOS-ZKZCYXTQSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- QJSFUOBKBXVTMN-UHFFFAOYSA-N C=C.P(O)(O)=O Chemical compound C=C.P(O)(O)=O QJSFUOBKBXVTMN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- JHKYFAAAOYOHHX-UHFFFAOYSA-N ac1oc8os Chemical compound OC(=O)CC(C(O)=O)[P+]([O-])=O JHKYFAAAOYOHHX-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical class OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 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 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 239000008096 xylene 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
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- Liquid Allzwec cleaning agents for use in the household and in commercial enterprises have taken their place in the past decade because they are simple and easy to use.
- the agents are usually marketed as preferably aqueous concentrates. They can already be identified as such, i.e. Apply undiluted, on a damp absorbent cloth of any texture or a sponge, with which the hard surfaces made of metal, painted wood, plastic, ceramic products such as porcelain, tiles, tiles and the like, are wiped away, thereby removing dust, greasy dirt and stains. It is desired that this surface treatment in turn does not leave any detergent stains and strips and does not require any aftertreatment, for example with a cloth soaked in clear water, that is to say moist.
- Such liquid all-purpose detergents generally consist of concentrated solutions of various anionic surfactant mixtures, but auci mixtures of anionic and nonionic surfactants are known. Among other things, you will in DE 27 09 690, DE 2840 463, EP 71 411, DE 39 43 070 and DE 41 34 973.
- alkyl glycosides which can be used here are understood to mean compounds with preferably an average of less than two glucose or xylose units per alkyl radical, in particular those with about 1 to 1.6 glucose or xylose units.
- Alkyl means not only, but preferably the residues of the fatty alcohols produced by hydrogenation of natural fatty acids, which are wholly or predominantly saturated, but which can also include unsaturated portions. They have about 8 to 18, in particular essentially about 8 to 14, carbon atoms.
- the alkyl polyglycosides are prepared either by direct reaction of glucose or xylose with the corresponding fatty alcohol or by acetalization of short-chain glycosides, preferably butyl glycosides, with the corresponding alcohol. The composition of the individual products is shown in the table below:
- Their share in the total mixture can be about 0.1 to 30, preferably about 1 to 28% by weight.
- Suitable anionic surfactants are those of the sulfonate and / or sulfate type.
- Surfactants of the sulfonate type are alkylbenzenesulfonates (Cg_i5-alkyl), mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation group , further alkanesulfonates which can be obtained from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, esters of ⁇ -sulfofatty acids, for example the ⁇ -sulfonic acids from hydrogenated alkyl esters of coconut, palm kernel or tallow fatty acids.
- the agents according to the invention are
- the preferred surfactants of the sulfate type for ecological reasons are the sulfuric acid monoesters of primary C12-C18, preferably C12-C14 alcohols and those of corresponding secondary alcohols.
- Sulfated fatty acid alkanols, sulfated fatty acid monoglycerides or sulfated reaction products of about 1-5 moles of ethylene oxide are also suitable with primary or secondary fatty alcohols.
- preference is given to derivatives of fatty acids, since they are of natural origin and represent renewable raw materials.
- anionic surfactants can be present in the form of their alkali metal, alkaline earth metal, in particular magnesium and ammonium salts, and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- organic bases such as mono-, di- or triethanolamine.
- the sodium salts are usually preferred.
- alkyl polyglycol ethers with an HLB value greater than 10, preferably 11, can also be added as further nonionic surfactants.
- Alkyl radicals of these alkyl polyglycol ethers are to be understood as meaning the alkyl chains from fatty alcohols of natural or synthetic origin and from oxo alcohols.
- These alkyl polyglycol ethers can be used in a ratio of approximately 0.1 to 5, preferably approximately 0.5 to 3, based on a part of the alkyl polyglucosides or xylosides named according to the invention. The total amount of nonionic surfactants is retained.
- African complex formers are used, which are preferably in the form of their alkali or amine salts, in particular the sodium and potassium salts.
- the alkali hydroxides also belong to the framework substances here.
- inorganic substances which can optionally be added to the agents according to the invention are, for example, bicarbonates, carbonates, borates, silicates or polyphosphates such as pentasodium tri-phosphate, pyrophosphates or orthophosphates.
- bicarbonates carbonates
- borates silicates
- polyphosphates such as pentasodium tri-phosphate, pyrophosphates or orthophosphates.
- the latter salts containing phosphorus ions should advantageously not be used.
- the organic complexing agents of the aminopolycarboxylic acid type include, inter alia, nitrilotriacetic acid, ethylenedia intetraacetic acid. right, N-hydroxyethyl ethylene diaminetriacetic acid.
- polyphosphonic acids methylene diphosphonic acids, l-hydroxyethane-l, l-diphosphonic acid, propane-l, l, 3-triphosphonic acid, butane-l, 2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, copolymers of vinylphosphonic acid and acrylic acid, ethane -l, 2, dicarboxy-l, 2-diphosphonic acid, ethane-1,2-dicarboxy-1,2-dihydroxydiphosphonic acid, phosphosuccinic acid, l-aminoethane-1,2-diphosphonic acid, a inotri- (ethylene phosphonic acid), methyl ino- or Ethyl ino-di- (m
- carboxylic acids are often, if not exclusively, suggested as examples of N- or P-free and therefore preferred mono- or polyvalent carboxylic acids or their salts as builder substances.
- a large number of these carboxylic acids have a complexing ability for calcium. These include e.g. B. citric acid, tartaric acid, benzene hexacarboxylic acid, tetrahydrofuran tetracarboxylic acid, gluconic acid, glutaric acid, succinic acid, adipic acid, polyacrylic acids and copolymers or mixtures thereof.
- household cleaning agents are generally neutral to slightly alkaline, i. H. their aqueous working solutions at application concentrations of usually about 1 to 20, preferably about 5 to 15 g / l of water or aqueous solution have a pH in the range from 6.0 to 10.5, preferably 7.0 to 9.5, own, it may be necessary to add small amounts of acidic and / or alkaline components, also as buffers, to regulate the pH.
- Suitable acidic substances are conventional inorganic or organic acids or acidic salts, such as, for example, hydrochloric acid or sulfuric acid, lactic acid, polycarboxylic acids, such as. As citric acid, tartaric acid, glutaric acid, succinic acid, adipic acid or mixtures thereof and the like.
- organic or inorganic compounds such as z. B. sodium hydroxide, alkanolamines, namely mono-, di- or triethanolamine or ammonia.
- solubilizers individually or as a mixture with one another, can be incorporated, which in addition to water-soluble organic solvents such as, in particular, low-molecular aliphatic alcohols with 1-4 carbon atoms, also the so-called hydrotropic substances of the lower alkylarylsulfonate type, for example toluene, xylene or cumene sulfonates or short-chain alkyl sulfates such as octyl sulfate or the short-chain homologues of other surfactants, including alkyl glycosides with less than 8 carbon atoms in the alkyl radical, for example butyl glucoside.
- the anionic representatives can also be in the form of their sodium and / or potassium and / or alkylamino salts.
- Water-soluble organic solvents can also be used as solubilizers, in particular those with boiling points above 75 ° C., for example the ethers from the same or different polyhydric alcohols or the partial ethers from polyhydric alcohols. These include, for example, di- or triethylene glycol polyglycerols and the partial ethers of ethylene glycol, propylene glycol, butylene glycol or glycerol with aliphatic monohydric alcohols containing 1-6 carbon atoms in the molecule.
- ketones such as acetone, methyl ethyl ketone and aliphatic, cycloaliphatic and aromatic hydrocarbons, and also the terpene alcohols.
- the weight ratio of surfactant to solvent or solubilizer can be 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1.
- the claimed agents can contain, as other conventional constituents, additives to colorants and fragrances, preservatives and polymeric cleaning enhancers, for example according to DE 2840463.
- a frame formulation of the concentrates according to the invention can thus have a total of approximately the following basic composition:
- Alkyl polyglycosides about 0.1 to 30, preferably about 1 to 28 further surfactants: about 2.0 to 20, preferably about 5 to 15 builder substances: about 0.1 to 7, preferably about 0.5 to 3 surfactants: solvents / solubilizers: 1: 0 to 1: 2, preferably 1: 0.05 to 1: 1
- Dyes / fragrances / cleaning enhancers small amounts of preservatives: small amounts of water: the remainder to 100
- the cleaning agent to be tested was placed on an artificially soiled plastic surface.
- a detergent with 10 wt .-% surfactant a mixture of petroleum jelly (R), fatty acid glycerol esters and pigments was used as the test.
- the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
- the test area. was with Coated 10 ml of the detergent solution. After ten wiping movements with a plastic sponge, the cleaned test surface was kept under running water and the loose dirt was removed.
- the cleaning effect ie the degree of whiteness of the plastic surface cleaned in this way, was determined using a Microcolor color difference measuring device from Dr. Measured for a long time.
- the cleaning performance of the formulations given in the following examples was based on the cleaning performance mentioned above. Standard formulations related, which was set to 100%. The pH of the formulations was adjusted to about 7.0 either with sodium hydroxide solution or with citric acid, as required.
- FAES Ci2 / i4-fatty alcohol ether sulfate with about 2 E0, Na salt (Texapon (R) N)
- FAS Ci2 / 14 ⁇ f r et 'ta lkoholsulfat, Na salt
- APG-8 Cs-alkyl polyglucoside (1.6 GE)
- APG-10 CiQ alkyl polyglucoside (1.6 GE)
- APG-12 Ci2 alkyl polyglucoside (1.4 GE)
- APG-14 Ci4 alkyl polyglucoside (1.4 GE)
- Polyox ( R ) WSR 205 polyethylene glycol MG 600000
- GE glucose units per alkyl group
- XE xylose units per alkyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
L'invention concerne des concentrés liquides servant à nettoyer des surfaces dures et qui sont à base de solutions aqueuses de tensioactifs anioniques et de tensioactifs non ioniques, d'adjuvants de lavage organiques et/ou inorganiques, de solvants solubles dans l'eau ou de solubiliseurs, ainsi que d'autres constituants classiques utilisés dans ce type de nettoyants. Ces concentrés liquides contiennent comme tensioactifs non ioniques des alkylpolyglycosides de la formule ROXx, où R = C8-C18, de préférence C8-C14, 0 = oxygène et x vaut environ entre 1 et 2, de préférence entre 1 et 1,6, Z désignant une unité glucose et/ou de préférence une unité xylose.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934311159 DE4311159A1 (de) | 1993-04-05 | 1993-04-05 | Verwendung flüssiger Konzentrate zum Reinigen harter Oberflächen |
| DE4311159 | 1993-04-05 | ||
| PCT/EP1994/000972 WO1994022998A1 (fr) | 1993-04-05 | 1994-03-28 | Utilisation de concentres liquides pour nettoyer des surfaces dures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0693115A1 true EP0693115A1 (fr) | 1996-01-24 |
Family
ID=6484791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94912548A Ceased EP0693115A1 (fr) | 1993-04-05 | 1994-03-28 | Utilisation de concentres liquides pour nettoyer des surfaces dures |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0693115A1 (fr) |
| CZ (1) | CZ216195A3 (fr) |
| DE (1) | DE4311159A1 (fr) |
| HU (1) | HUT71623A (fr) |
| PL (1) | PL310983A1 (fr) |
| WO (1) | WO1994022998A1 (fr) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9509452D0 (en) * | 1995-05-10 | 1995-07-05 | Unilever Plc | Light duty cleaning composititon |
| DE19717950A1 (de) * | 1997-04-29 | 1998-11-05 | Henkel Kgaa | Tensidgemische |
| FR2807435B1 (fr) * | 2000-04-06 | 2004-02-06 | Seppic Sa | Nouveaux derives de polyxylosides, procede pour leur preparation, composition en comportant et utilisation comme agents tensioactifs |
| FR2820317B1 (fr) * | 2001-02-05 | 2005-07-29 | Seppic Sa | Utilisation d'alkylpolyxylosides comme agents emulsionnants pour la preparation d'emulsions eau-dans-huile |
| FR2830445B1 (fr) * | 2001-10-05 | 2004-08-13 | Seppic Sa | Utilisation d'alkylpolyxylosides comme agents ameliorant le toucher cosmetique d'emulsions huile-dans-eau contenant un polymere |
| FR2831539B1 (fr) * | 2001-10-25 | 2005-02-11 | Seppic Sa | Utilisation d'alkylpolyglycosides comme agents emulsionnants pour la preparation d'emulsion huile-dans eau contenant des charges ou pigments mineraux, et emulsions huile-dans-eau contenant de tels alkylpolyglycosides |
| DE102004025859A1 (de) * | 2004-05-24 | 2005-12-22 | Henkel Kgaa | Kit aus Schwamm und Reiniger |
| DE102012221021A1 (de) * | 2012-11-19 | 2014-05-22 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittel mit Alkylpolypentosiden |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0070074B2 (fr) * | 1981-07-13 | 1997-06-25 | THE PROCTER & GAMBLE COMPANY | Compositions moussantes contenant des agents tensio-actifs |
| US4683074A (en) * | 1985-04-26 | 1987-07-28 | A. E. Staley Manufacturing Company | Stability and compatibility of glycosides in acid systems |
-
1993
- 1993-04-05 DE DE19934311159 patent/DE4311159A1/de not_active Withdrawn
-
1994
- 1994-03-28 WO PCT/EP1994/000972 patent/WO1994022998A1/fr not_active Ceased
- 1994-03-28 HU HU9502904A patent/HUT71623A/hu unknown
- 1994-03-28 EP EP94912548A patent/EP0693115A1/fr not_active Ceased
- 1994-03-28 CZ CZ952161A patent/CZ216195A3/cs unknown
- 1994-03-28 PL PL94310983A patent/PL310983A1/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9422998A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| HU9502904D0 (en) | 1995-12-28 |
| PL310983A1 (en) | 1996-01-22 |
| CZ216195A3 (en) | 1996-01-17 |
| WO1994022998A1 (fr) | 1994-10-13 |
| HUT71623A (en) | 1996-01-29 |
| DE4311159A1 (de) | 1994-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0712436B1 (fr) | Produits de lavage ou de nettoyage faiblement moussants | |
| EP1126019B1 (fr) | Utilisation d' une composition aqueuse multiphasique pour nettoyage des surfaces dures | |
| EP0808354B1 (fr) | Detergents aqueux s'epaississant pour surfaces dures | |
| EP0876460B1 (fr) | Agent de nettoyage pour surfaces dures | |
| WO2001021752A1 (fr) | Produit nettoyant aqueux a plusieurs phases | |
| WO1991009926A1 (fr) | Detergent liquide pour surfaces dures | |
| EP0693115A1 (fr) | Utilisation de concentres liquides pour nettoyer des surfaces dures | |
| DE19853720A1 (de) | Allzweckreiniger mit diquaternärem-Polysiloxan | |
| EP0928829B1 (fr) | Nettoyage de surfaces dures à l'aide d'agents rhéopexiques en milieu aqueux | |
| WO2000039270A1 (fr) | Produit de nettoyage aqueux multiphase | |
| EP0197480A2 (fr) | Procédé de nettoyage manuel d'objets à surfaces dures | |
| EP0574431B1 (fr) | Procede pour le nettoyage de tapis et moquettes | |
| EP0609303B1 (fr) | Detergent liquide concentre pour surfaces dures | |
| DE19644252A1 (de) | Reinigung harter Oberflächen mit rheopexen wäßrigen Reinigungsmitteln | |
| WO1990005770A2 (fr) | Produit a nettoyer liquide pour surfaces dures | |
| DE4316740A1 (de) | Polymerhaltige Universalreinigungsmittel | |
| DE19908563C2 (de) | Reinigungsmittel für harte Oberflächen | |
| DE10037405A1 (de) | Reinigung harter Oberflächen mit verdickenden wäßrigen Reinigungsmitteln |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19950927 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL PT SE |
|
| 17Q | First examination report despatched |
Effective date: 19960124 |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED |
|
| 18R | Application refused |
Effective date: 19970810 |