CN108738297A - 降低工业产品的微生物侵染的方法 - Google Patents
降低工业产品的微生物侵染的方法 Download PDFInfo
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- CN108738297A CN108738297A CN201780014245.1A CN201780014245A CN108738297A CN 108738297 A CN108738297 A CN 108738297A CN 201780014245 A CN201780014245 A CN 201780014245A CN 108738297 A CN108738297 A CN 108738297A
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- methyl
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- 238000000034 method Methods 0.000 title claims abstract description 74
- 208000015181 infectious disease Diseases 0.000 title abstract description 8
- 230000000813 microbial effect Effects 0.000 title abstract description 8
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 claims abstract description 14
- 239000003973 paint Substances 0.000 claims description 22
- 239000003139 biocide Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- -1 5- chloro-2-methyl -4- isothiazolinone Oxazoline Chemical compound 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- 244000005700 microbiome Species 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005839 Tebuconazole Substances 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 239000006013 carbendazim Substances 0.000 claims description 6
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 claims description 6
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 6
- 235000018417 cysteine Nutrition 0.000 claims description 6
- YSRSBDQINUMTIF-UHFFFAOYSA-N decane-1,2-diol Chemical compound CCCCCCCCC(O)CO YSRSBDQINUMTIF-UHFFFAOYSA-N 0.000 claims description 6
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 claims description 6
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 6
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical class CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 claims description 6
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 6
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical class CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- XNRNJIIJLOFJEK-UHFFFAOYSA-N sodium;1-oxidopyridine-2-thione Chemical compound [Na+].[O-]N1C=CC=CC1=S XNRNJIIJLOFJEK-UHFFFAOYSA-N 0.000 claims description 6
- 235000010199 sorbic acid Nutrition 0.000 claims description 6
- 239000004334 sorbic acid Substances 0.000 claims description 6
- 229940075582 sorbic acid Drugs 0.000 claims description 6
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- GZAGDUDNLKUBSZ-UHFFFAOYSA-N 1-bromo-2-nitropropane Chemical class BrCC(C)[N+]([O-])=O GZAGDUDNLKUBSZ-UHFFFAOYSA-N 0.000 claims description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 5
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005510 Diuron Substances 0.000 claims description 5
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 5
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 239000011505 plaster Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 claims description 5
- UUGLSEIATNSHRI-UHFFFAOYSA-N 1,3,4,6-tetrakis(hydroxymethyl)-3a,6a-dihydroimidazo[4,5-d]imidazole-2,5-dione Chemical compound OCN1C(=O)N(CO)C2C1N(CO)C(=O)N2CO UUGLSEIATNSHRI-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229960004365 benzoic acid Drugs 0.000 claims description 4
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims description 4
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229940043810 zinc pyrithione Drugs 0.000 claims description 4
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims description 4
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 claims description 3
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 claims description 3
- 229960003415 propylparaben Drugs 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 150000003577 thiophenes Chemical class 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical class C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 claims description 2
- FBJAGEQLOUPXHL-UHFFFAOYSA-N 1-sulfanylethanesulfonic acid Chemical class CC(S)S(O)(=O)=O FBJAGEQLOUPXHL-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 108010024636 Glutathione Proteins 0.000 claims description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000005018 casein Substances 0.000 claims description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021240 caseins Nutrition 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000005068 cooling lubricant Substances 0.000 claims description 2
- 239000010730 cutting oil Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000005553 drilling Methods 0.000 claims description 2
- 229940009662 edetate Drugs 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 229960003180 glutathione Drugs 0.000 claims description 2
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- 239000010985 leather Substances 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical group OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 2
- 235000018102 proteins Nutrition 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims description 2
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002026 pyrithione Drugs 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims 3
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims 1
- SNDJGKIVHKOEHY-UHFFFAOYSA-M S(=S)(=O)(O)O.S[Na] Chemical compound S(=S)(=O)(O)O.S[Na] SNDJGKIVHKOEHY-UHFFFAOYSA-M 0.000 claims 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 238000006356 dehydrogenation reaction Methods 0.000 claims 1
- 238000004043 dyeing Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical group [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims 1
- 239000004246 zinc acetate Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 68
- 239000000203 mixture Substances 0.000 description 14
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 13
- UNRLFGKAPAPARO-UHFFFAOYSA-N 5-chloro-2-methyl-1,2-thiazolidine Chemical compound CN1CCC(Cl)S1 UNRLFGKAPAPARO-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 230000002335 preservative effect Effects 0.000 description 6
- BNZJGVGWJIZQGJ-UHFFFAOYSA-N 3-chloro-2-methyl-1,2-thiazolidine Chemical compound CN1SCCC1Cl BNZJGVGWJIZQGJ-UHFFFAOYSA-N 0.000 description 4
- SYRYCMSRILEZNI-UHFFFAOYSA-N 5-chloro-2-methyl-3h-1,2-thiazole Chemical class CN1CC=C(Cl)S1 SYRYCMSRILEZNI-UHFFFAOYSA-N 0.000 description 4
- 206010012442 Dermatitis contact Diseases 0.000 description 4
- 206010020751 Hypersensitivity Diseases 0.000 description 4
- MUCRYNWJQNHDJH-OADIDDRXSA-N Ursonic acid Chemical compound C1CC(=O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C MUCRYNWJQNHDJH-OADIDDRXSA-N 0.000 description 4
- 208000010247 contact dermatitis Diseases 0.000 description 4
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- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 208000030961 allergic reaction Diseases 0.000 description 3
- 230000001717 pathogenic effect Effects 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical class CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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Abstract
本发明涉及一种用于降低产品的微生物侵染的方法,在其范围内使用5‑氯‑2‑甲基‑4‑异噻唑啉‑3‑酮,其基于5‑氯‑2‑甲基‑4‑异噻唑啉‑3‑酮的总量计含有在0至2重量%的范围内的2‑甲基‑4‑异噻唑啉‑3‑酮,其在后续方法步骤中至少大部分被分解。本发明方法的特征还在于,在进一步的方法步骤中,使用至少一种其他组分用于对产品的二次防腐。
Description
技术领域
本发明涉及一种用于降低产品的微生物侵染的方法,在其范围内使用5-氯-2-甲基-4-异噻唑啉-3-酮,基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计含有在0至2重量%的范围内的2-甲基-4-异噻唑啉-3-酮,其在后续工艺步骤中至少大部分被分解。本发明方法的特征还在于,在另一工艺步骤中,使用至少一种其他组分用于对产品二次防腐。
背景技术
通常使用天然或可生物降解的原料生产工业的、尤其是水性的产品,例如漆、清漆、乳液和化妆品。在这里,这些原料和用作溶剂的水经常被细菌、酵母和真菌等病原菌污染。如果在制造这些产品时不进行防腐,那么它们在生产后一天就已经具有很高的病原菌数量。
为了确保这些产品符合卫生要求并因此确保工业产品的耐久性,向产品添加所谓的生物灭杀剂。这些生物灭杀剂之一是5-氯-2-甲基异噻唑啉-3-酮(CMIT)。其具有良好的杀生物效果,但在实际处理中具有各种不同的缺点。例如,该化合物可能会对处理它的人引发过敏。
为了克服这种尽管非常有效的、但也带有对于最终用户的缺点的CMIT的缺陷,在EP1005271B1中所公开的异噻唑啉酮2-甲基异噻唑啉-3-酮(MIT)和1,2-苯并异噻唑啉-3-酮(BIT)的混合物自90年代开始就用作生物灭杀剂组合物。此混合物由Thor GmbH(联邦德国Speyer)作为MBS出售并在今日成为水基漆和灰泥罐内防腐的标准。此生物灭杀剂组合物具有的优点是,通过两种异噻唑啉酮的针对性选择,将高效率与同5-氯-2-甲基异噻唑啉-3-酮相比显著较低的致敏可能性结合在一起。
尽管另选MBS作为5-氯-2-甲基异噻唑啉-3-酮的替代品,但是在使用MBS进行防腐的产品中仍含有MIT,它对于过敏性患者或对高敏感度的人来说可引起接触性湿疹和气源性接触性湿疹。
然而,由于上述情况,不可能完全放弃有效的防腐剂。
在公开的德国专利申请DE 198 10 819 A1中提出了一种可能的解决方案。该文献涉及制备适合用于对异噻唑啉酮有过敏性反应的人的漆组合物的方法。在该方法的范围内,将其中含有异噻唑啉酮的漆组合物与试剂如硫代硫酸钠混合,所述试剂可通过化学反应将异噻唑啉酮分解,使得可产生对于有过敏性反应的人无害的后续产品。
然而,缺点是,根据所描述的方法不定量地和可逆地破坏异噻唑啉酮,特别是MIT,所以它们仍然包含在产品和后续产品中,并继续会对有过敏反应的人产生问题,更具体地是会对具有高敏感度的人引起接触性湿疹或气源性接触性湿疹。在本发明人进行的实验范围内能够表明,例如,在水性乳胶漆中所含的2-甲基异噻唑啉-3-酮借助硫代硫酸钠既不能定量地也不能不可逆地破坏。
发明内容
因此,本发明的一个目的是提供一种方法,借助于该方法能够制备出也适用于对5-氯-2-甲基异噻唑啉-3-酮或2-甲基异噻唑啉-3-酮有过敏性反应的人,更具体地适用于对5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮高度敏感的人的产品。在该方法的范围内,不会放弃使用5-氯-2-甲基异噻唑啉-3-酮。
该目的通过一种降低产品微生物侵染的方法实现,所述方法包括以下步骤:
(A)提供产品,
(B)加入1ppm至100ppm的5-氯-2-甲基-4-异噻唑啉-3-酮,其含有在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮,基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计,
(C)用至少一种分解5-氯-2-甲基-4-异噻唑啉酮(isothiazolon)的化合物分解5-氯-2-甲基-4-异噻唑啉-3-酮,和
(D)添加至少一种选自如下的生物灭杀剂:用量为1ppm至1000ppm的1,2-苯并异噻唑啉-3-酮、用量为1至2500ppm的2,2-二溴-3-氰基(nitril)丙酰胺、2,2-二溴丙二酰胺、四羟甲基乙炔二脲、甲醛、戊二醛、苯氧基乙醇、用量为1ppm至2000ppm的2-溴-2-硝基丙烷-1,3-二醇、用量为1ppm至2500ppm的吡啶硫酮锌、吡啶硫酮钠、苄醇、3-碘代炔丙基-N-丁基氨基甲酸酯、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮、用量为1ppm至500ppm的银源、2-甲基-1,2-苯并异噻唑啉-3-酮、乙基己基甘油、1,2-辛二醇、1,2-己二醇、1,2-戊二醇、1,2-癸二醇、对羟基苯甲酸丙基酯、山梨酸、苯甲酸、抗坏血酸、苯扎氯铵、二甲基二(十二烷基)氯化铵、特丁净、敌草隆、多菌灵、戊唑醇和邻苯基苯酚。
根据一个实施方案,本发明不涉及这样的方法,即在其范围内制备含有50ppm的1,2-苯并异噻唑啉-3-酮、100ppm的2-巯基吡啶-N-氧化锌(吡啶硫酮锌)和10ppm的氧化锌的乳胶漆。
本发明使得可以使用特别有效的5-氯-2-甲基异噻唑啉-3-酮在生产过程中对所述产品防腐,并在上市前对其进行处理,使得最终产品中不再含有5-氯-2-甲基异噻唑啉-3-酮,其可能会对5-氯-2-甲基异噻唑啉-3-酮高度敏感的人造成问题。在产品生产期间使用5-氯-2-甲基异噻唑啉-3-酮的优点在于,借助于这种非常有效的广谱生物灭杀剂,可以有效地灭活被各个产品的单个组分所携带的微生物,从而在针对性地破坏5-氯-2-甲基异噻唑啉-3-酮后获得几乎无菌产品,该产品可以借助于生物灭杀剂二次防腐。
在方法步骤(A)中提供的产品通常是选自如下的产品:漆、室内漆、清漆、釉料、灰泥、内墙灰泥、乳液、胶乳、聚合物分散体、木质素磺酸盐、白垩浆、矿物浆、陶瓷物料、粘合剂、密封剂、含酪蛋白产品、含淀粉产品、沥青乳液、表面活性剂溶液、燃料、清洁剂、颜料膏和颜料分散体、油墨、平版印刷液、增稠剂、化妆品、卫浴用品(Toilettenartikeln)、水回路、纸加工液、皮革制造液、纺织品制造液、钻孔和切削油、液压油和冷却润滑液。
术语“产品”应理解为意指最终产品和中间产品。根据本发明一个特别优选的实施方案,产品是聚合物乳液或室内漆或内墙灰泥的前体。前体是指在投放市场之前对这些产品进行处理,使得产品中所含的5-氯-2-甲基异噻唑啉-3-酮理想地定量分解。
根据本发明的另一个实施方案,产品是水基产品。水含量通常为5至99.9重量%。
在方法步骤(A)中提供的产品优选地特征在于:它具有含量在0ppm至1ppm的范围内的2-甲基-4-异噻唑啉-3-酮,基于所述产品计。根据本发明的一个优选实施方案,在方法步骤(A)中提供的产品具有含量在0.1ppm至0ppm范围内的2-甲基-4-异噻唑啉-3-酮,根据一个特别优选的实施方案含量为0ppm。由于2-甲基-4-异噻唑啉-3-酮在提供的产品中可忽略的较少含量,可以借助于本发明的方法通过使用具有如上所定义的2-甲基-4-异噻唑啉-3-酮含量的5-氯-2-甲基-4-异噻唑啉-3-酮,获得经防腐的产品,其防腐剂可以在任何所需的时间点以简单的方式针对性分解,由此能够获得不含5-氯-2-甲基-4-异噻唑啉-3-酮和2-甲基-4-异噻唑啉-3-酮的(最终)产品。
5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的大规模工业生产是已知的并且可以以各种方式来进行,它们都获得5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的混合物。例如,US3,849,430A描述了两种替代方案,其提供5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的混合物。如上所述,在5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的混合物中含有的2-甲基异噻唑啉-3-酮不能被容易地破坏,使得用2-甲基异噻唑啉-3-酮防腐的(最终)产品可能对过敏患者或对2-甲基异噻唑啉-3-酮具有高度敏感性的人造成问题。规避该问题的一种途径是完全放弃使用含有2-甲基异噻唑啉-3-酮的5-氯-2-甲基异噻唑啉-3-酮。
然而,本发明使得能够以一种完全新型的混合物形式进一步使用5-氯-2-甲基异噻唑啉-3-酮,该混合物含有基于5-氯-2-甲基-4-异噻唑啉-3-酮计在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮,优选地各自基于5-氯-2-甲基-4-异噻唑啉-3-酮计在0至1重量%的范围内。
如上所述,5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的大规模工业生产总是提供5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的混合物。虽然具有低5-氯-2-甲基异噻唑啉-3-酮含量的含2-甲基异噻唑啉-3-酮的生物灭杀剂组合物是可商购的,但基于5-氯-2-甲基-4-异噻唑啉-3-酮总量计含有在0至2重量%范围内2-甲基-4-异噻唑啉-3-酮的5-氯-2-甲基-4-异噻唑啉-3-酮组合物不是可商购的。
借助于已知的分离方法例如色谱法、萃取或分级沉淀,本领域技术人员可以从5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉-3-酮的混合物制备在方法步骤(B)中使用的具有根据本发明所需的少量2-甲基-4-异噻唑啉-3-酮的5-氯-2-甲基-4-异噻唑啉-3-酮。借助于本领域技术人员已知的方法,例如通过定量HPLC,可确定5-氯-2-甲基-4-异噻唑啉-3-酮的纯度或其在相应的产品中的含量。
基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计具有在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮含量的5-氯-2-甲基异噻唑啉-3-酮,在方法步骤(B)中以1ppm至100ppm范围、优选5ppm至50ppm范围、特别优选5ppm至30ppm范围内的量添加到相应的产品中。
本发明一般性地涉及降低产品的微生物侵染的方法。“用于降低产品的微生物侵染”在本发明意义上是指,通过在产品中加入一定量的基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计具有在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮含量的5-氯-2-甲基异噻唑啉-3-酮,证明延缓或完全抑制了在相应的产品中包含的微生物的微生物生长。
在方法步骤(B)中,向产品中添加1ppm至100ppm、优选5ppm至50ppm、特别优选5ppm至30ppm的5-氯-2-甲基-4-异噻唑啉-3-酮,其基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计具有在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮含量,优选具有在0至1重量%范围内的2-甲基-4-异噻唑啉-3-酮含量。结果,获得用5-氯-2-甲基-4-异噻唑啉-3-酮防腐的产品,其防腐剂可以在任何所需的时间点以简单的方式在方法步骤(C)中针对性地分解。
在方法步骤(C)的范围中,在方法步骤(B)中添加的5-氯-2-甲基-4-异噻唑啉-3-酮借助于至少一种分解5-氯-2-甲基-4-异噻唑啉酮的化合物进行分解或降解。
优选地,5-氯-2-甲基-4-异噻唑啉酮在此这样地降解或分解,使得5-氯-2-甲基-4-异噻唑啉酮在产品中的含量在添加至少一种分解5-氯-2-甲基-4-异噻唑啉酮的化合物之后的少于24小时内仅仅还在0ppm至0.5ppm的范围内,优选在0ppm至0.1ppm的范围内,基于总产品计。
“5-氯-2-甲基-4-异噻唑啉酮的分解”在本发明范围中是指,5-氯-2-甲基-4-异噻唑啉酮在方法步骤(C)中在最高至24小时的时间段内、优选在0.5至12小时的时间段内、特别优选在2至6小时的时间段内不可逆地分解或降解,使得在该时间段之后基于产品计5-氯-2-甲基-4-异噻唑啉酮的含量在0ppm至0.5ppm的范围内,特别优选在0ppm至0.1ppm的范围内。
在最高至24小时的时间段内在此是指,在方法步骤(B)中添加的5-氯-2-甲基-4-异噻唑啉酮在从与至少一种分解5-氯-2-甲基-4-异噻唑啉酮的化合物接触的时间点起24小时内被分解,从而该24小时之后5-氯-2-甲基-4-异噻唑啉酮的总含量基于产品计在0ppm至0.5ppm的范围内。
在本发明的范围内,用于分解5-氯-2-甲基-4-异噻唑啉酮的试剂是指通过化学反应分解或失活5-氯-2-甲基-4-异噻唑啉酮的化合物。用于分解5-氯-2-甲基-4-异噻唑啉酮的试剂导致在上述定义的时间段内在产品中含有的5-氯-2-甲基-4-异噻唑啉酮的含量降低到0ppm至0.5ppm的范围内。这些试剂或化合物是本领域已知的。因此,选择它们是本领域技术人员常做的。
根据本发明的一种优选的实施方案,用于分解5-氯-2-甲基-4-异噻唑啉酮的试剂是至少一种硫代化合物。
根据本发明的一种特别优选的实施方案,在方法步骤(C)中使用的用于分解5-氯-2-甲基-4-异噻唑啉酮的试剂是至少一种选自由半胱氨酸、巯基乙醇、巯基丙酸、巯基丙酸甲酯、谷胱甘肽、硫代乙醇酸盐、硫代硫酸钠、亚硫酸氢钠、吡啶硫酮、巯基吡啶、二硫苏糖醇、巯基乙磺酸盐和甲醛次硫酸钠组成的组的化合物。根据本发明的一种特别优选的实施方案,用于分解5-氯-2-甲基-4-异噻唑啉酮的试剂是半胱氨酸。
用于分解5-氯-2-甲基-4-异噻唑啉酮的化合物的量或其与产品中所含的5-氯-2-甲基-4-异噻唑啉酮的摩尔比可在宽范围内变化。通常,5-氯-2-甲基-4-异噻唑啉酮与至少一种将其分解的化合物的摩尔比在20:1至1:20、优选在5:1至1:5、特别优选在2:1至1:2的范围内。
根据本发明的一种优选实施方案,根据本发明的方法的特征在于,为了在方法步骤(C)中分解5-氯-2-甲基-4-异噻唑啉酮,基于产品计使用量为1至200ppm、优选5ppm至25ppm的半胱氨酸。
在方法步骤(C)中5-氯-2-甲基-4-异噻唑啉-3-酮分解后,该产品理想地不受微生物侵袭,但可能由于缺乏防腐剂尚未被防护免受新引入的病原体的侵害。
根据本发明的一种替代性实施方案,在根据本发明的方法的范围内,在方法步骤(D)中,将待防腐产品中的pH值调节至在9.5至12范围内的pH值,优选调节至在10.5至11.5范围内的pH值。优选通过添加NaOH和/或KOH来调节pH值。在乳胶漆的情况下,申请人能够表明,在5-氯-2-甲基-4-异噻唑啉-3-酮分解并将pH值调节至在9.5至12范围内的pH值之后,其具有至少6个月的储存稳定性。
根据本发明,在方法步骤(D)中在产品中添加至少一种选自如下的其他生物灭杀剂:用量为1ppm至1000ppm的1,2-苯并异噻唑啉-3-酮、用量为1ppm至2500ppm的2,2-二溴-3-氰基(nitril)丙酰胺、2,2-二溴丙二酰胺、四羟甲基乙炔二脲、甲醛、戊二醛、苯氧基乙醇、用量为1ppm至2000ppm的2-溴-2-硝基丙烷-1,3-二醇、用量为1ppm至2500ppm的吡啶硫酮锌、吡啶硫酮钠、苄醇、3-碘代炔丙基-N-丁基氨基甲酸酯、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮、用量为1ppm至500ppm的银源、2-甲基-1,2-苯并异噻唑啉-3-酮、乙基己基甘油、1,2-辛二醇、1,2-己二醇、1,2-戊二醇、1,2-癸二醇、对羟基苯甲酸丙基酯、山梨酸、苯甲酸、抗坏血酸、苯扎氯铵、二甲基二(十二烷基)氯化铵、特丁净、敌草隆、多菌灵、戊唑醇和邻苯基苯酚。上述量是指各生物灭杀剂相对于产品的比例。
在本发明的范围内,“至少一种另外的生物灭杀剂”是指在方法步骤(D)中加入单一生物灭杀剂或更多,即两种、三种、四种、五种或更多种生物灭杀剂。
根据本发明的一种优选实施方案,在方法步骤(D)中,向产品中添加至少一种另外的生物灭杀剂,其选自2,2-二溴丙二酰胺、四羟甲基乙炔二脲、甲醛、戊二醛、苯氧基乙醇、吡啶硫酮钠、苄醇、3-碘代炔丙基-N-丁基氨基甲酸酯、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮、2-甲基-1,2-苯并异噻唑啉-3-酮、乙基己基甘油、1,2-辛二醇、1,2-己二醇、1,2-戊二醇、1,2-癸二醇、对羟基苯甲酸丙酯、山梨酸、苯甲酸、抗坏血酸、苯扎氯铵、二甲基二(十二烷基)氯化铵、丁唑酸、敌草隆、多菌灵、戊唑醇和邻苯基苯酚。在本发明的范围内,银源是指选自元素银、银盐、氧化银、氢氧化银、硫酸银、氯化银、银络合物及其组合的化合物。
在方法步骤(D)中加入的生物灭杀剂用于对最初用5-氯-2-甲基-4-异噻唑啉-3-酮防腐的产品进行二次防腐。通过在方法步骤(C)中5-氯-2-甲基-4-异噻唑啉-3-酮的分解,尽管产品理想地没有微生物侵染,但可能由于缺乏防腐剂还没有充分被防护免受新引入的病原体的侵害。为了确保这种防护,在方法步骤(D)中加入至少一种来自上述组的生物灭杀剂。
根据本发明的一种优选实施方案,根据本发明的方法的特征在于在方法步骤(D)中添加:
1,2-苯并异噻唑啉-3-酮,用量为1ppm至1,000ppm,
2,2-二溴-3-氰基丙酰胺,用量为1ppm至2,500ppm,
2-溴-2-硝基丙烷-1,3-二醇,用量为1ppm至2,000ppm,
吡啶硫酮锌,用量为1ppm至2,500ppm,
元素银,用量为1ppm至500ppm,
氧化银,用量为1ppm至500ppm,
氯化银,用量为1ppm至500ppm,
2,2-二溴丙二酰胺,用量为1ppm至2,500ppm,
四羟甲基乙炔二脲,用量为5ppm至5,000ppm,
甲醛,用量为5ppm至500ppm,
戊二醛,用量为5ppm至500ppm,
苯氧基乙醇,用量为10ppm至25,000ppm,
2-溴-2-硝基丙烷-1,3-二醇,用量为1ppm至2,000ppm,
吡啶硫酮钠,用量为1ppm至2,500ppm,
苄基醇,用量为10ppm至25,000ppm,
3-碘代炔丙基-N-丁基氨基甲酸酯,用量为10ppm至2,000ppm,
2-正辛基-4-异噻唑啉-3-酮,用量为10ppm至2,000ppm,
4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,用量为10ppm至2,000ppm,
2-甲基-1,2-苯并异噻唑啉-3-酮,用量为1ppm至1,000ppm,
乙基己基甘油,用量为10ppm至20,000ppm,
1,2-戊二醇,用量为10ppm至20,000ppm,
1,2-己二醇,用量为10ppm至20,000ppm,
1,2-辛二醇,用量为10ppm至2,000ppm,
1,2-癸二醇,用量为10ppm至20,000ppm,
对羟基苯甲酸丙酯,用量为10ppm至10,000ppm,
山梨酸,用量为10ppm至10,000ppm,
苯甲酸,用量为10ppm至10,000ppm,
抗坏血酸,用量为10ppm至10,000ppm,
苯扎氯铵,用量为10ppm至5,000ppm,
二甲基二(十二烷基)氯化铵,用量为10ppm至5,000ppm,
特丁净,用量为10ppm至2,000ppm,
敌草隆,用量为10ppm至2,000ppm,
多菌灵,用量为10ppm至2,000ppm,
戊唑醇,用量为10ppm至2,000ppm,和/或
邻苯基苯酚,用量为1ppm至10,000ppm,
分别基于待防腐的产品计。
在根据本发明的方法的范围内,可以在方法步骤(D)中将上述生物灭杀剂之一以对于待防腐产品规定的量添加到产品中。然而,也可以在方法步骤(D)中将上述生物灭杀剂的多种,即两种、三种、四种和更多种以对于待防腐产品规定的量添加到产品中。
根据本发明的一种优选实施方案,在进一步的方法步骤即方法步骤(E)中,将选自乙二胺四乙酸盐、锌源和锂源的组分加入到产品中。在此过程中,在方法步骤(D)中加入另外的组分产生提高在方法步骤(D)中加入的至少一种生物灭杀剂的有效性的作用。
根据本发明的一种优选实施方案,在方法步骤(E)中,将至少一种选自氧化锌、氯化锌、硫酸锌、磷酸锌、氢氧化锌、碳酸锌、抗坏血酸锌、脱氢醋酸锌和羧酸锌的锌化合物以基于产品计10ppm至5,000ppm的量加入到产品中。根据本发明的一种特别优选的实施方案,在方法步骤(E)中,将至少一种选自氧化锌、氯化锌和碳酸锌的锌化合物加入到产品中,优选地以基于产品计10ppm至5,000ppm的量。
根据本发明的优选实施方案,在方法步骤(E)中以基于产品计10ppm至5,000ppm的量加入至少一种锂化合物,优选选自氯化锂、碳酸锂、硫酸锂和氢氧化锂。在根据本发明的一种特别优选的实施方案中,在方法步骤(E)中,将至少一种选自氯化锂和碳酸锂的锂化合物加入到产品中,优选地以基于产品计10ppm至5,000ppm的量。
将参考以下实施例更详细地描述本发明:
向不含防腐剂的苯乙烯丙烯酸酯分散体中加入20ppm的具有<1重量%的2-甲基异噻唑啉-3-酮含量的5-氯-2-甲基异噻唑啉-3-酮。然后将如此防腐的苯乙烯丙烯酸酯分散体用于制备水基乳胶漆。生产的漆(Farbe)具有以下组成:
25.7重量%的水
0.2重量%的丙烯酸酯基的润湿剂和分散剂
0.2重量%的矿物油基消泡剂
2.0重量%的软水剂(多磷酸钠)
0.2重量%的氨
4.0重量%的氧化钛(颜料)
51.0重量%的碳酸钙(填料)
5.0重量%的滑石(填料)
0.4重量%的纤维素醚
2.0重量%的有机溶剂,用以降低最低成膜温度
9.0重量%的用20ppm的5-氯-2-甲基异噻唑啉-3-酮防腐的苯乙烯丙烯酸酯分散体
20ppm的具有<1重量%的2-甲基异噻唑啉-3-酮含量的5-氯-2-甲基异噻唑啉-3-酮。
借助于微生物学研究,在乳胶漆中没有检测到微生物生长,而在单个组分中可以检测到微生物生长。因此,高效的5-氯-2-甲基异噻唑啉-3-酮足以完全杀死通过漆的各个组分引入的微生物。
为了从含有显著量的5-氯-2-甲基异噻唑啉-3-酮的乳胶漆制备在其中所含的5-氯-2-甲基异噻唑啉-3-酮和2-甲基异噻唑啉酮方面对于过敏患者无害的漆,将这些异噻唑啉-3-酮通过加入50ppm的半胱氨酸(基于乳胶漆计)分解。在3小时后,通过HPLC已不再能在乳胶漆中检测到5-氯-2-甲基异噻唑啉-3-酮。
尽管如此制备的漆由于使用有效的广谱杀菌剂5-氯-2-甲基异噻唑啉-3-酮而没有微生物,但是由于生物灭杀剂被半胱氨酸分解,对于在储存期间可能进入漆中的新引入的微生物,它是容易被侵染的。
因此,为了保护漆在储存期间免受这种微生物侵染,基于乳胶漆计加入50ppm的2-甲基-1,2-苯并异噻唑啉-3-酮和10ppm的氧化锌,以进行二次防腐。这样制备的漆具有至少6个月的储存稳定性。
Claims (10)
1.一种降低产品的微生物浸染的方法,其包括如下步骤:
(A)提供产品,和
(B)加入1ppm至100ppm的5-氯-2-甲基-4-异噻唑啉-3-酮,其具有在0至2重量%范围内的2-甲基-4-异噻唑啉-3-酮,基于5-氯-2-甲基-4-异噻唑啉-3-酮的总量计,
(C)借助至少一种分解5-氯-2-甲基-4-异噻唑啉酮的化合物分解5-氯-2-甲基-4-异噻唑啉-3-酮,和
(D)添加至少一种选自如下的生物灭杀剂:用量为1ppm至1000ppm的1,2-苯并异噻唑啉-3-酮、用量为1ppm至2500ppm的2,2-二溴-3-氰基丙酰胺、2,2-二溴丙二酰胺、四羟甲基乙炔二脲、甲醛、戊二醛、苯氧基乙醇、用量为1ppm至2000ppm的2-溴-2-硝基丙烷-1,3-二醇、用量为1ppm至2500ppm的吡啶硫酮锌、吡啶硫酮钠、苄醇、3-碘代炔丙基-N-丁基氨基甲酸酯、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮、用量为1ppm至500ppm的银源、2-甲基-1,2-苯并异噻唑啉-3-酮、乙基己基甘油、1,2-辛二醇、1,2-己二醇、1,2-戊二醇、1,2-癸二醇、对羟基苯甲酸丙基酯、山梨酸、苯甲酸、抗坏血酸、苯扎氯铵、二甲基二(十二烷基)氯化铵、特丁净、敌草隆、多菌灵、戊唑醇和邻苯基苯酚。
2.根据权利要求1所述的方法,其特征在于,在方法步骤(D)中添加:
2,2-二溴丙二酰胺,用量为1ppm至2,500ppm,
四羟甲基乙炔二脲,用量为5ppm至5,000ppm,
甲醛,用量为5ppm至500ppm,
戊二醛,用量为5ppm至500ppm,
苯氧基乙醇,用量为10ppm至25,000ppm,
2-溴-2-硝基丙烷-1,3-二醇,用量为1ppm至2,000ppm,
吡啶硫酮钠,用量为1ppm至2,500ppm,
苄基醇,用量为10ppm至25,000ppm,
3-碘代炔丙基-N-丁基氨基甲酸酯,用量为10ppm至2,000ppm,
2-正辛基-4-异噻唑啉-3-酮,用量为10ppm至2,000ppm,
4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,用量为10ppm至2,000ppm,2-甲基-1,2-苯并异噻唑啉-3-酮,用量为1ppm至1,000ppm,
元素银,用量为1ppm至500ppm,
氧化银,用量为1ppm至500ppm,
氯化银,用量为1ppm至500ppm,
乙基己基甘油,用量为10ppm至20,000ppm,
1,2-戊二醇,用量为10ppm至20,000ppm,
1,2-己二醇,用量为10ppm至20,000ppm,
1,2-辛二醇,用量为10ppm至2,000ppm,
1,2-癸二醇,用量为10ppm至20,000ppm,
对羟基苯甲酸丙酯,用量为10ppm至10,000ppm,
山梨酸,用量为10ppm至10,000ppm,
苯甲酸,用量为10ppm至10,000ppm,
抗坏血酸,用量为10ppm至10,000ppm,
苯扎氯铵,用量为10ppm至5,000ppm,
二甲基二(十二烷基)氯化铵,用量为10ppm至5,000ppm,
特丁净,用量为10ppm至2,000ppm,
敌草隆,用量为10ppm至2,000ppm,
多菌灵,用量为10ppm至2,000ppm,
戊唑醇,用量为10ppm至2,000ppm,和/或
邻苯基苯酚,用量为1ppm至10,000ppm,
分别基于待防腐的产品计。
3.根据权利要求1所述的方法,其特征在于,在一种替代性方法步骤(D)中,将产品中的pH值调节至pH 9至12的范围。
4.根据权利要求1至3中任一项的方法,其特征在于,在进一步的方法步骤(E)中,添加选自乙二胺四乙酸盐、锌源和锂源的组分。
5.根据权利要求4所述的方法,其特征在于,基于产品计,以10ppm至5000ppm的量加入锌源,并且是选自由氧化锌、氯化锌、硫酸锌、磷酸锌、氢氧化锌、碳酸锌、抗坏血酸锌、脱氢醋酸锌和羧酸锌所组成的组的至少一种化合物。
6.根据权利要求4所述的方法,其特征在于,基于产品计,以10ppm至5000ppm的量加入锂源,并且是选自由氯化锂、碳酸锂、硫酸锂和氢氧化锂所组成的组中的至少一种化合物。
7.根据权利要求1至6中任一项所述的方法,其特征在于,在方法步骤(C)中使用一种化合物,其选自由半胱氨酸、巯基乙醇、巯基丙酸、巯基丙酸甲酯、谷胱甘肽、硫代乙醇酸盐、硫代硫酸钠、亚硫酸氢钠、吡啶硫酮、巯基吡啶、二硫苏糖醇、巯基乙磺酸盐和甲醛次硫酸钠组成的组。
8.根据权利要求1至7中任一项的方法,其特征在于,在方法步骤
(A)中,提供具有在0ppm至1ppm范围内的2-甲基-4-异噻唑啉-3-酮含量的产品。
9.根据权利要求1至8中任一项所述的方法,其特征在于,所述产品选自如下产品:漆、室内漆、清漆、釉料、灰泥、内墙灰泥、乳液、胶乳、聚合物分散体、木质素磺酸盐、白垩浆、矿物浆、陶瓷物料、粘合剂、密封剂、含酪蛋白产品、含淀粉产品、沥青乳液、表面活性剂溶液、燃料、清洁剂、颜料膏和颜料分散体、油墨、平版印刷液、增稠剂、化妆品、卫浴用品、水回路、纸加工液、皮革制造液、纺织品制造液、钻孔和切削油、液压油和冷却润滑液。
10.一种根据权利要求1至9中任一项所述的方法制备的产品。
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