JP5550661B2 - Transparent film-forming liquid antibacterial agent composition - Google Patents
Transparent film-forming liquid antibacterial agent composition Download PDFInfo
- Publication number
- JP5550661B2 JP5550661B2 JP2011545936A JP2011545936A JP5550661B2 JP 5550661 B2 JP5550661 B2 JP 5550661B2 JP 2011545936 A JP2011545936 A JP 2011545936A JP 2011545936 A JP2011545936 A JP 2011545936A JP 5550661 B2 JP5550661 B2 JP 5550661B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- acid
- aqueous solution
- water
- agent composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims description 103
- 239000007788 liquid Substances 0.000 title claims description 28
- 239000003242 anti bacterial agent Substances 0.000 title description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- 230000000844 anti-bacterial effect Effects 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 43
- 229920000620 organic polymer Polymers 0.000 claims description 36
- 230000002209 hydrophobic effect Effects 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 20
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000004308 thiabendazole Substances 0.000 claims description 19
- 235000010296 thiabendazole Nutrition 0.000 claims description 19
- 229960004546 thiabendazole Drugs 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 9
- 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 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005839 Tebuconazole Substances 0.000 claims description 3
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical compound C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
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- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
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- -1 amine salt Chemical class 0.000 description 14
- 235000019645 odor Nutrition 0.000 description 13
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 11
- 239000011976 maleic acid Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 9
- 229940121375 antifungal agent Drugs 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
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- 239000000758 substrate Substances 0.000 description 7
- 229920003169 water-soluble polymer Polymers 0.000 description 7
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 6
- 125000004018 acid anhydride group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 230000005923 long-lasting effect Effects 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- PZBPKYOVPCNPJY-UHFFFAOYSA-N 1-[2-(allyloxy)-2-(2,4-dichlorophenyl)ethyl]imidazole Chemical compound ClC1=CC(Cl)=CC=C1C(OCC=C)CN1C=NC=C1 PZBPKYOVPCNPJY-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000855 fungicidal effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical class 0.000 description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005795 Imazalil Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000004645 aluminates Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000656 anti-yeast Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical group [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical group OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 229960002125 enilconazole Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 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 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、透明性及び抗菌効果の持続性に優れた透明膜形成液状抗菌剤組成物に関し、より詳細には、アルコール成分の含有量が低いため、溶媒臭が低減され、かつ、安全性の高い透明性及び抗菌効果の持続性に優れた透明膜形成液状抗菌剤組成物及びその製造方法に関する。また本発明は、さらにｐＨの調整をすることによって、光安定性を付与した透明膜形成液状抗菌剤組成物及びその製造方法に関する。
本願は、２００９年１２月１５日に出願された日本国特許出願第２００９−２８４４２８号及び２０１０年７月２６日に出願された日本国特許出願第２０１０−１６７４９５号に対し優先権を主張し、その内容をここに援用する。The present invention relates to a transparent film-forming liquid antibacterial agent composition that is excellent in transparency and durability of antibacterial effect, and more specifically, since the content of the alcohol component is low, the solvent odor is reduced and the safety is improved. The present invention relates to a transparent film-forming liquid antibacterial composition excellent in transparency and durability of antibacterial effect, and a method for producing the same. The present invention also relates to a transparent film-forming liquid antibacterial composition imparted with light stability by further adjusting the pH and a method for producing the same.
This application claims priority to Japanese Patent Application No. 2009-284428 filed on December 15, 2009 and Japanese Patent Application No. 2010-167495 filed on July 26, 2010, The contents are incorporated here.
現在の住環境は、エアコンによる冷暖房効率の向上や、花粉の室内への進入を防ぐ等の観点から、高度に密閉化されている。そのため、浴室内や台所まわり、窓のサッシといった水分の多い場所にあっては、真菌や細菌等の菌類が繁殖し易く、このような菌類の繁殖を防止するべく、様々な抗菌剤がこれまでに開発されてきた。 The current living environment is highly sealed from the viewpoints of improving the efficiency of air conditioning with air conditioners and preventing pollen from entering the room. For this reason, fungi such as fungi and bacteria can easily grow in bathrooms, around kitchens, and in windows with sashes, and various antibacterial agents have been used in the past to prevent such fungi from growing. Has been developed.
しかし、浴室内や台所まわり、窓のサッシ等の場所は水分に曝されやすいため、それらの場所に抗菌剤を散布又は塗布しても、水分によって抗菌成分が溶出してしまい、抗菌効果があまり持続せず、持続的な効果を得るためには、抗菌剤をかなり頻繁に散布しなければならなかった。そこで、抗菌剤の持続性を向上させる試みがなされてきた。例えば特許文献１には、防カビ成分に加えて、撥水性被膜形成成分として、炭素鎖長１０〜１４のジアルキルジメチルアンモニウム塩を配合することによって、防カビ剤の防カビ効果の持続性を向上させることが記載されている。しかし、抗菌剤の持続性は十分とはいえなかった。 However, places in the bathroom, around the kitchen, window sashes, etc. are easily exposed to moisture, so even if an antibacterial agent is sprayed or applied to those places, the antibacterial components are eluted by the moisture, and the antibacterial effect is not much. Antibiotics had to be sprayed fairly frequently to achieve lasting and lasting effects. Thus, attempts have been made to improve the durability of antibacterial agents. For example, Patent Document 1 improves the sustainability of the antifungal effect of the antifungal agent by adding a dialkyldimethylammonium salt having a carbon chain length of 10 to 14 as a water repellent film forming component in addition to the antifungal component. Is described. However, the durability of the antibacterial agent was not sufficient.
また、防カビ剤としてよく用いられるチアベンダゾール等は、アルコールや水等の溶媒への溶解度が低いので、適当な溶媒に単に溶解させてその溶解液を散布又は塗布しても、すぐに析出して白濁してしまうため、持続的な防カビ効果を得ることはより困難であった。加えて、特に屋内用途では、チアベンダゾール等の析出又は白濁は、清潔感を損われた印象を見る者に与えるため、実用上の使用感には問題があった。 In addition, thiabendazole, which is often used as an antifungal agent, has low solubility in solvents such as alcohol and water, so even if it is simply dissolved in an appropriate solvent and sprayed or applied, the solution immediately precipitates. Since it becomes cloudy, it has been more difficult to obtain a continuous antifungal effect. In addition, particularly in indoor applications, precipitation or white turbidity of thiabendazole or the like gives a person who sees an impression of impaired cleanliness, and there is a problem in practical use.
一方、特許文献２には、藻類やカビ類が繁殖して生物汚染が進んでいる建築物外装部材に、少ない工程で短時間かつ経済的に塗布でき、生物汚染した部分を容易に改修しうる水系防藻（カビ）塗料として、「合成樹脂ラテックスを主成分とする建築物外装部材用の水系防藻（カビ）塗料であって、樹脂固形分１００重量部に対して０．０１〜１０重量部の防藻剤又は防カビ剤、及び０〜５重量部の増粘剤を配合し、かつ樹脂固形分濃度を１〜３０重量％に調整することを特徴とする水系防藻（カビ）塗料」が記載されている。
特許文献２には、該塗料を透明塗膜とし得ることが記載されているが、これは樹脂固形分濃度を低く抑えて膜厚を薄くすることによりなし得る（特許文献２の段落番号００３１の記載参照）ものである。On the other hand, in Patent Document 2, it can be applied in a short time and economically to a building exterior member in which algae and fungi have propagated and biological contamination has progressed, and the biologically contaminated portion can be easily repaired. As a water-based anti-algae (mold) paint, “a water-based anti-algae (mold) paint for building exterior members mainly composed of synthetic resin latex, and 0.01 to 10 weights per 100 parts by weight of resin solids. A water-based anti-algae (mold) paint comprising a part of an anti-algae or fungicide and 0 to 5 parts by weight of a thickener, and the resin solid content concentration is adjusted to 1 to 30% by weight Is described.
Patent Document 2 describes that the coating material can be a transparent coating film, but this can be achieved by reducing the resin solid content concentration and reducing the film thickness (see paragraph No. 0031 of Patent Document 2). See description).
発明者らはすでに、透明性及び抗菌効果の持続性が高い透明膜形成液状抗菌剤組成物を提案しており（特許文献３）、実施例には、組成物全体に対して４９．６〜９９．６質量％のエタノールを含有する組成物が記載されている。かかる組成物は、高い透明性や持続抗菌性を示すものの、溶媒含量が高いために溶媒臭（アルコール臭）があるという問題があった。また、引火性液体であるアルコールの含量が高いために、安全性の問題も懸念されていた。 The inventors have already proposed a transparent film-forming liquid antibacterial composition having a high transparency and a long lasting antibacterial effect (Patent Document 3). A composition containing 99.6% by weight of ethanol is described. Although such a composition exhibits high transparency and long-lasting antibacterial properties, it has a problem that it has a solvent odor (alcohol odor) due to its high solvent content. Moreover, since the content of alcohol, which is a flammable liquid, is high, there is a concern about safety problems.
このような状況下において、透明性及び透明性の持続性が高く、かつ抗菌効果の持続性も高い透明膜形成抗菌剤組成物において、溶媒臭が低く、安全性の高い透明膜形成抗菌剤組成物が求められていた。 Under such circumstances, a transparent film-forming antibacterial agent composition having a low solvent odor and a high safety in a transparent film-forming antibacterial agent composition having high transparency and high transparency persistence and high antibacterial effect persistence Things were sought.
本発明は、刺激性が低く、対象に散布した場合の透明性及び透明性の持続性が高く、かつ抗菌効果の持続性も高い透明膜形成液状抗菌剤組成物において、溶媒臭が低く、安全性の高い透明膜形成液状抗菌剤組成物を提供することを課題とする。以下、「透明膜形成液状抗菌剤組成物」を、単に「抗菌剤組成物」という。 The present invention is a transparent film-forming liquid antibacterial composition that has low irritation, high transparency when applied to a subject, high transparency, and high antibacterial effect. It is an object of the present invention to provide a highly transparent transparent film-forming liquid antibacterial agent composition. Hereinafter, the “transparent film-forming liquid antibacterial agent composition” is simply referred to as “antibacterial agent composition”.
本発明者等は、予め、疎水性部位を有する有機ポリマーと抗菌成分とアルコール系溶媒とを含有する溶解液を作成しておき、該溶解液を水に分散させることで、アルコール系溶媒の含量を低減した抗菌剤組成物を作製でき、かかる方法によって、溶媒臭が低く、安全性の高い抗菌剤組成物を得られることを見出し、また発明者等は、抗菌成分の酸性水溶液と疎水性部位を有する有機ポリマーのアルカリ性水溶液とを混合することにより、エタノール等の溶媒を使用しなくても、透明で、抗菌効果の持続性の高い抗菌剤組成物を製造することができることを見出し、本発明を完成するに至った。 The inventors previously prepared a solution containing an organic polymer having a hydrophobic site, an antibacterial component, and an alcohol solvent, and dispersing the solution in water to obtain a content of the alcohol solvent. Found that an antibacterial composition having a low solvent odor and a high safety can be obtained by such a method, and the inventors have found that an aqueous solution of an antibacterial component and a hydrophobic site It was found that an antibacterial agent composition that is transparent and has a long lasting antibacterial effect can be produced by mixing with an alkaline aqueous solution of an organic polymer having an organic solvent, without using a solvent such as ethanol. It came to complete.
すなわち本発明は、
（１）疎水性部位を有する有機ポリマー、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分、水、及び、組成物全体に対して０〜２０質量％未満のアルコール系溶媒を含有する透明膜形成液状抗菌剤組成物、
（２）疎水性部位を有する有機ポリマーがスチレン−マレイン酸共重合体又はアクリル酸重合体であることを特徴とする上記（１）に記載の透明膜形成液状抗菌剤組成物、
（３）酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分がチアベンダゾールあるいはイマザリルであることを特徴とする、上記（１）又は（２）に記載の透明膜形成液状抗菌剤組成物、及び
（４）ｐＨが６．５以上であることを特徴とする上記（１）〜（３）のいずれかに記載の透明膜形成液状抗菌剤組成物に関する。That is, the present invention
(1) An organic polymer having a hydrophobic site, acid-soluble, and an antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, water, and less than 0 to less than 20% by mass with respect to the entire composition Transparent film-forming liquid antibacterial agent composition containing an alcohol solvent of
(2) The transparent film-forming liquid antibacterial composition according to (1) above, wherein the organic polymer having a hydrophobic site is a styrene-maleic acid copolymer or an acrylic acid polymer,
(3) The transparent film according to (1) or (2) above, wherein the antibacterial component that is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less is thiabendazole or imazalil. The liquid antibacterial composition for liquid formation and (4) the liquid antibacterial composition for transparent film formation according to any one of (1) to (3) above, wherein the pH is 6.5 or more.
また本発明は、
（５）（ａ）疎水性部位を有する有機ポリマー、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分及び組成物全体に対して０〜２０質量％未満のアルコール系溶媒を含有する溶解液を作製する工程、及び
（ｂ）工程（ａ）で得た溶解液を水に分散させる工程
を有することを特徴とする、上記（１）〜（４）のいずれかに記載のアルコール系溶媒を含有する透明膜形成液状抗菌剤組成物の製造方法、
（６）工程（ｂ）が、水を攪拌下、水に工程（ａ）で得た溶解液を添加する工程であることを特徴とする、上記（５）に記載の製造方法に関する。The present invention also provides
(5) (a) An organic polymer having a hydrophobic site, acid-soluble, and an antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less and less than 0 to less than 20% by mass based on the whole composition Any of the above (1) to (4), comprising a step of preparing a solution containing an alcohol solvent, and a step (b) of dispersing the solution obtained in step (a) in water. A method for producing a transparent film-forming liquid antibacterial agent composition containing the alcohol solvent according to claim 1,
(6) The method according to (5), wherein the step (b) is a step of adding the solution obtained in the step (a) to water while stirring the water.
さらに本発明は、
（７）酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分を含有するｐＨ６以下の水溶液（Ａ）と、アルカリ可溶性で、かつ、疎水性部位を有する有機ポリマーを含有するｐＨ７以上の水溶液（Ｂ）とを混合することを特徴とする、上記（１）〜（４）のいずれかに記載のアルコール系溶媒を含有しない透明膜形成液状抗菌剤組成物の製造方法、
（８）水溶液（Ａ）を水溶液（Ｂ）に攪拌しながら添加することを特徴とする、上記（７）に記載の透明膜形成液状抗菌剤組成物の製造方法、
（９）水溶液（Ａ）を水溶液（Ｂ）に連続的に滴下することを特徴とする、上記（７）又は（８）に記載の透明膜形成液状抗菌剤組成物の製造方法に関する。Furthermore, the present invention provides
(7) An acid-soluble aqueous solution (A) having a pH of 6 or less containing an antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and an alkali-soluble organic polymer having a hydrophobic site A transparent film-forming liquid antibacterial agent composition containing no alcohol solvent according to any one of the above (1) to (4), which is mixed with an aqueous solution (B) containing at least pH 7 containing Method,
(8) The method for producing a transparent film-forming liquid antibacterial composition according to (7) above, wherein the aqueous solution (A) is added to the aqueous solution (B) with stirring.
(9) The method for producing a transparent film-forming liquid antibacterial composition according to (7) or (8) above, wherein the aqueous solution (A) is continuously dropped into the aqueous solution (B).
本発明の抗菌剤組成物は、疎水性部位を有する有機ポリマーと、抗菌成分と、水と、任意にアルコール系溶媒とを含有する組成物であって、アルコール系溶媒を含む場合、当該アルコール系溶媒が組成物全体に対して２０質量％未満であることを特徴とする。 The antibacterial agent composition of the present invention is a composition comprising an organic polymer having a hydrophobic site, an antibacterial component, water, and optionally an alcohol solvent, and when the alcohol solvent is included, the alcohol It is characterized in that the solvent is less than 20% by mass with respect to the whole composition.
（疎水性部位を有する有機ポリマー）
本発明の疎水性部位を有する有機ポリマー（以下、単に「有機ポリマー」ということがある。）の疎水性部位としては、特に制限されないが、例えばメチル基、エチル基、ｎ−プロピル基、ｓ−プロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基等のアルキル基；ビニル基、ビニリデン基、エチニル基等のアルケニル基；フェニル基；ナフチル基、アントラニル基等の縮合多環フェニル基；ビフェニル基、ターフェニル基等の疎水性置換基を有するフェニル基；その他の非極性基等を例示することができる。(Organic polymer with hydrophobic sites)
The hydrophobic moiety of the organic polymer having a hydrophobic moiety of the present invention (hereinafter sometimes simply referred to as “organic polymer”) is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an s- Alkyl groups such as propyl group, n-butyl group, s-butyl group and t-butyl group; alkenyl groups such as vinyl group, vinylidene group and ethynyl group; phenyl group; condensed polycyclic phenyl groups such as naphthyl group and anthranyl group A phenyl group having a hydrophobic substituent such as a biphenyl group or a terphenyl group; and other nonpolar groups.
本発明の有機ポリマーは、親水性部位を有していなくてもよいが、より優れた透明性、透明性の持続性、及び抗菌効果の持続性の観点から、さらに親水性部位を有していることが好ましい。
親水性部位としては、特に制限されないが、例えばカルボキシル基及びその金属塩若しくはアミン塩；スルホン酸基及びその金属塩若しくはアミン塩；スルホアミド基；アミド基；アミノ基；イミノ基；ヒドロキシ基；４級アミノ基；オキシアミノ基；ジアゾニウム基；グアニジン基；ヒドラジン基；リン酸基；ケイ酸基；アルミン酸基；ニトリル基；チオアルコール基；フェノール基；アルコール基；エーテル基；その他の極性基等を挙げることができ、中でもカルボキシル基、スルホン酸基、スルホアミド基、アミド基、アミノ基、イミノ基、ヒドロキシ基、４級アミノ基、オキシアミノ基、ジアゾニウム基、グアニジン基、ヒドラジン基、リン酸基、ケイ酸基、アルミン酸基、ニトリル基、チオアルコール基、フェノール基、アルコール基及びエーテル基からなる群から選ばれるいずれか１種又は２種以上を好ましく例示することができる。The organic polymer of the present invention may not have a hydrophilic part, but from the viewpoint of better transparency, transparency persistence, and antibacterial effect persistence, it further has a hydrophilic part. Preferably it is.
The hydrophilic site is not particularly limited, and examples thereof include a carboxyl group and a metal salt or amine salt thereof; a sulfonic acid group and a metal salt or amine salt thereof; a sulfoamide group; an amide group; an amino group; an imino group; An amino group; an oxyamino group; a diazonium group; a guanidine group; a hydrazine group; a phosphoric acid group; a silicic acid group; an aluminate group; a nitrile group; a thioalcohol group; a phenol group; an alcohol group; an ether group; Among them, carboxyl group, sulfonic acid group, sulfoamide group, amide group, amino group, imino group, hydroxy group, quaternary amino group, oxyamino group, diazonium group, guanidine group, hydrazine group, phosphoric acid group, Silicic acid group, aluminate group, nitrile group, thioalcohol group, phenol group, alcohol It can be preferably exemplified one kind or two or more species selected from the group consisting of groups and ether groups.
本発明に用いる有機ポリマーとして、より具体的には、親水性部位を有するモノマーと疎水性部位を有するモノマーとの共重合体や、親水性部位及び疎水性部位を有するモノマーの重合体等を挙げることができる。
なお、透明性及び透明性の持続性がより高く、かつ抗菌効果の持続性もより高い膜が得られる観点から、親水性部位を有するモノマーと疎水性部位を有するモノマーとの共重合体は、両モノマーのランダム共重合体又は交互共重合体であることが好ましい。More specifically, examples of the organic polymer used in the present invention include a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part, and a polymer of a monomer having a hydrophilic part and a hydrophobic part. be able to.
From the viewpoint of obtaining a film having higher transparency and transparency persistence and higher persistence of antibacterial effect, a copolymer of a monomer having a hydrophilic part and a monomer having a hydrophobic part is: A random copolymer or an alternating copolymer of both monomers is preferred.
疎水性部位を有するモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、（イソ）プロピル（メタ）アクリレート、（イソ又はターシャリー）ブチル（メタ）アクリレート、（イソ）アミル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、（イソ）オクチル（メタ）アクリレート、（イソ）デシル（メタ）アクリレート、（イソ）ドデシル（メタ）アクリレート、（イソ）ステアリル（メタ）アクリレート等の炭素数１〜１８のアルキル基を有する（メタ）アクリル酸エステル類；スチレン、ビニルトルエン、２−メチルスチレン、クロロスチレン等のスチレン系モノマー、ベンジル（メタ）アクリレート等の芳香環含有モノマー等を挙げることができ、中でもスチレン、ビニルトルエン、２−メチルスチレン、クロロスチレン等のスチレン系モノマーを好ましく挙げることができ、スチレンをより好ましく挙げることができる。なお、（メタ）アクリレートとは、メタクリレート又はアクリレートを示している。 Examples of the monomer having a hydrophobic site include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meta) ) Acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) stearyl (meth) ) (Meth) acrylic acid esters having an alkyl group of 1 to 18 carbon atoms such as acrylate; styrene monomers such as styrene, vinyltoluene, 2-methylstyrene, chlorostyrene, and aromatic rings such as benzyl (meth) acrylate List monomers Can be, among others, vinyltoluene, 2-methylstyrene, can be preferably exemplified a styrene-based monomer such as chlorostyrene, it can be mentioned more preferably styrene. In addition, (meth) acrylate has shown the methacrylate or the acrylate.
親水性部位を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸等のモノ又はジカルボン酸モノマー；２−アクリロイルオキシエチル−２−ヒドロキシエチルフタル酸、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２−ヒドロキシエチルメタクリレート、Ｎ−メチロールアクリルアミド等水酸基含有モノマー；スチレンスルホン酸ナトリウム、スルホン化イソプレン等スルホン酸基含有モノマー；アクリルアミド、メタクリルアミド等のアミド化合物モノマー等を挙げることができ、中でもアクリル酸、メタクリル酸、マレイン酸、イタコン酸等のモノまたはジカルボン酸モノマーを好ましく挙げることができ、マレイン酸、イタコン酸等のジカルボン酸モノマーをより好ましく挙げることができる。
なお、本発明に用いる親水性部位を有するモノマーは、モノマーの状態では親水性部位を有していなくてもよく、抗菌剤組成物中に含まれる有機ポリマーの状態で親水性部位を有していればよい。例えば、無水マレイン酸モノマーは、親水性部位を有さないが、抗菌剤組成物中に含まれる有機ポリマーの状態において、無水マレイン酸の酸無水物基が加水分解により開環し、親水性部位であるカルボキシル基が生成していれば、親水性部位を有する有機ポリマーであるといえる。
マレイン酸、イタコン酸等のジカルボン酸モノマーの場合、有機ポリマーの状態でカルボキシル基を１つ、エステルを１つ有していればよいが、より優れた本発明の効果を得る観点から、カルボキシル基を２つ有していることが好ましい。Examples of the monomer having a hydrophilic portion include mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxy-3-phenoxy Examples thereof include hydroxyl group-containing monomers such as propyl acrylate, 2-hydroxyethyl methacrylate and N-methylol acrylamide; sulfonic acid group-containing monomers such as sodium styrene sulfonate and sulfonated isoprene; amide compound monomers such as acrylamide and methacrylamide. Preferred examples include mono- or dicarboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and more preferred examples include dicarboxylic acid monomers such as maleic acid and itaconic acid. It can be.
The monomer having a hydrophilic part used in the present invention may not have a hydrophilic part in the monomer state, and has a hydrophilic part in the state of an organic polymer contained in the antibacterial agent composition. Just do it. For example, the maleic anhydride monomer does not have a hydrophilic site, but in the state of the organic polymer contained in the antibacterial agent composition, the acid anhydride group of maleic anhydride is ring-opened by hydrolysis, resulting in a hydrophilic site. If the carboxyl group which is is produced | generated, it can be said that it is an organic polymer which has a hydrophilic region.
In the case of dicarboxylic acid monomers such as maleic acid and itaconic acid, it is sufficient to have one carboxyl group and one ester in the state of the organic polymer. From the viewpoint of obtaining the more excellent effects of the present invention, the carboxyl group It is preferable to have two.
親水性部位及び疎水性部位を有するモノマーとしては、例えば、Ｎ−エチル（メタ）アクリルアミド、Ｎ−シクロプロピル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−エチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ−メチル−Ｎ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、Ｎ−イソプロペニルピロリドン、Ｎ−イソプロペニルカプロラクタム、Ｎ−（メタ）アクリロイルピロリジン、Ｎ−（メタ）アクリロイルピペリジン等を挙げることができる。 Examples of the monomer having a hydrophilic part and a hydrophobic part include N-ethyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N- Examples include vinylpyrrolidone, N-vinylcaprolactam, N-isopropenylpyrrolidone, N-isopropenylcaprolactam, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine and the like.
本発明に用いる有機ポリマーとして、具体的には、スチレンマレイン酸共重合体（ＳＭＡ）やその誘導体を好ましく例示することができる。
スチレンマレイン酸共重合体としてはスチレン：マレイン酸のモル比が５：１〜１：１の化合物が好ましく、より好ましくは３：１〜２：１の化合物が用いられる。スチレンマレイン酸共重合体の誘導体とは、スチレンマレイン酸共重合体から誘導可能な化合物であって、本発明において、スチレンマレイン酸共重合体と同様に用いうるものを意味し、例えば、スチレン無水マレイン酸共重合体とアルコールを反応させることにより、無水マレイン酸部分の酸無水物基が開環され、モノエステル／モノカルボン酸基となっている共重合体や、スチレンマレイン酸共重合体の芳香族基の適当な位置に、スルフォニル基等の置換基を有する共重合体や、スチレン無水マレイン酸共重合体の無水マレイン酸部分がアミンによりイミド化された共重合体や、スチレン無水マレイン酸の酸無水物基が開環されて生じたエステル基やカルボン酸基がアミンによりイミド化された共重合体等が含まれる。
本発明に用いる有機ポリマーとして、より具体的には、スチレンマレイン酸コポリマー型（ＴＧ−７５０Ｗ：共栄社化学株式会社製）（スチレン無水マレイン酸重合体の無水マレイン酸部分の酸無水物基が開環され、モノエステル／モノカルボン酸基となっている共重合体）や、ＳＭＡエステルレジン（サートマー社製）（スチレン無水マレイン酸重合体の無水マレイン酸部分の酸無水物基が開環され、モノエステル／モノカルボン酸基となっている共重合体）や、ＳＭＡレジン：アンモニウム塩水溶液（サートマー社製）（スチレン無水マレイン酸重合体の無水マレイン酸部分の酸無水物基が加水分解され、ジカルボン酸基となっている共重合体）等を好ましく例示することができる。Specific examples of the organic polymer used in the present invention include styrene maleic acid copolymer (SMA) and derivatives thereof.
As the styrene maleic acid copolymer, a compound having a molar ratio of styrene: maleic acid of 5: 1 to 1: 1 is preferable, and a compound of 3: 1 to 2: 1 is more preferably used. The styrene maleic acid copolymer derivative means a compound that can be derived from a styrene maleic acid copolymer and can be used in the present invention in the same manner as the styrene maleic acid copolymer. By reacting the maleic acid copolymer with an alcohol, the acid anhydride group of the maleic anhydride moiety is ring-opened to form a monoester / monocarboxylic acid group copolymer or a styrene maleic acid copolymer. A copolymer having a substituent such as a sulfonyl group at an appropriate position of the aromatic group, a copolymer in which the maleic anhydride portion of the styrene maleic anhydride copolymer is imidized with an amine, or a styrene maleic anhydride And a copolymer in which an ester group or a carboxylic acid group formed by ring opening of the acid anhydride group is imidized with an amine.
More specifically, as the organic polymer used in the present invention, a styrene maleic acid copolymer type (TG-750W: manufactured by Kyoeisha Chemical Co., Ltd.) (the acid anhydride group of the maleic anhydride portion of the styrene maleic anhydride polymer is ring-opened) The copolymer is a monoester / monocarboxylic acid group) or an SMA ester resin (manufactured by Sartomer) (an acid anhydride group of the maleic anhydride portion of the styrene maleic anhydride polymer is ring-opened) A copolymer having an ester / monocarboxylic acid group) or an SMA resin: ammonium salt aqueous solution (manufactured by Sartomer) (an acid anhydride group of a maleic anhydride portion of a styrene maleic anhydride polymer is hydrolyzed to form a dicarboxylic acid). Preferred examples thereof include copolymers having acid groups.
有機ポリマーの分子量は、本発明の効果が得られる限り特に制限されないが、例えば数平均分子量が１,０００〜２００,０００の範囲内であることが好ましく、３,０００〜１００,０００の範囲内であることがより好ましい。
また、有機ポリマーの２０℃における水への溶解度は５０００ｐｐｍ以下であることが好ましく、２０００ｐｐｍ以下であることがより好ましい。
有機ポリマーとして、複数の有機ポリマーを混合して使用することもできる。The molecular weight of the organic polymer is not particularly limited as long as the effect of the present invention can be obtained. For example, the number average molecular weight is preferably in the range of 1,000 to 200,000, and is preferably in the range of 3,000 to 100,000. It is more preferable that
Further, the solubility of the organic polymer in water at 20 ° C. is preferably 5000 ppm or less, and more preferably 2000 ppm or less.
As the organic polymer, a plurality of organic polymers can be mixed and used.
（抗菌成分）
本発明に用いる抗菌成分は、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下であるものである。
当該条件を満たす限り制限はなく、例えば、公知の防カビ成分、抗細菌成分、抗酵母成分、抗ウイルス成分等（以下、単に抗菌成分ということがある）を使用することができる。
具体的には、抗菌成分として、チアベンダゾール（ＴＢＺ）、１−（２−（２，４−ジクロロフェニル）−２−（２−プロペニルオキシ）エチル）−１Ｈ−イミダゾール（イマザリル）、２−メトキシカルボニルアミノベンツイミダゾール（カルベンダジン）等のイミダゾール系化合物等、２−（４−チオシアノメチルチオ）ベンゾチアゾール（ＴＣＭＴＢ）等のチアゾール系化合物等、（ＲＳ）−１−ｐ−クロロフェニル−４，４−ジメチル−３−（１Ｈ−１，２，４−トリアゾール−１−イルメチル）ペンタン−３−オール（テブコナゾール）等のトリアゾール系化合物等を例示することができる。
これらの中で、チアベンダゾール、イマザリルが好ましく、特にチアベンダゾールが好ましい。(Antimicrobial component)
The antibacterial component used in the present invention is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less.
There is no limitation as long as the conditions are satisfied, and for example, known antifungal components, antibacterial components, antiyeast components, antiviral components and the like (hereinafter, sometimes simply referred to as antibacterial components) can be used.
Specifically, as an antibacterial component, thiabendazole (TBZ), 1- (2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl) -1H-imidazole (imazalyl), 2-methoxycarbonylamino Imidazole compounds such as benzimidazole (carbendazine), thiazole compounds such as 2- (4-thiocyanomethylthio) benzothiazole (TCMTB), (RS) -1-p-chlorophenyl-4,4-dimethyl- Examples thereof include triazole compounds such as 3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (tebuconazole).
Of these, thiabendazole and imazalyl are preferable, and thiabendazole is particularly preferable.
（水、アルコール系溶媒）
本発明の抗菌剤組成物には、水及び任意にアルコール系溶媒が含有される。
水としては、超純水、蒸留水、イオン交換水、水道水、市水、工業用水等のいずれを用いても良く、適宜選択しうる。
アルコール系溶媒は、メタノール、エタノール、イソプロピルアルコール等のＣ１〜Ｃ１０アルコール等が挙げられるが、エタノールを用いることが好ましい。アルコールは、１種単独でもよいし、２種以上のアルコールを含んでいてもよい。(Water, alcohol solvent)
The antimicrobial composition of the present invention contains water and optionally an alcohol solvent.
As water, any of ultrapure water, distilled water, ion-exchanged water, tap water, city water, industrial water, and the like may be used and may be appropriately selected.
Examples of the alcohol solvent include C1-C10 alcohols such as methanol, ethanol, and isopropyl alcohol, and ethanol is preferably used. One kind of alcohol may be used alone, or two or more kinds of alcohols may be contained.
（組成物）
本発明の抗菌剤組成物は、水、もしくは水とアルコール系溶媒の混合溶媒が溶媒成分であり、該溶媒成分に、疎水性部位を有する有機ポリマーと抗菌成分とが溶解及び／又は分散されているが、溶媒成分のうち、アルコール系溶媒は組成物に対して２０質量％未満である。アルコール系溶媒は、必ずしも含有しなければならないものではないため、この値に下限はない。(Composition)
In the antibacterial agent composition of the present invention, water or a mixed solvent of water and an alcohol solvent is a solvent component, and an organic polymer having a hydrophobic site and an antibacterial component are dissolved and / or dispersed in the solvent component. However, among the solvent components, the alcohol solvent is less than 20% by mass with respect to the composition. Since the alcohol solvent does not necessarily have to be contained, there is no lower limit to this value.
本発明の抗菌剤組成物は、塩化ビニル基板へスプレー塗布して形成した厚さ２０〜３００ｎｍの膜の、塗布から２４時間後のヘイズ率が５．０以下、好ましくは３．０以下、より好ましくは２．０以下である。
なお、ヘイズ率は、厚さ０．５ｍｍの透明塩化ビニール板（アクリサンデー社製、透明硬質塩化ビニール板、ヘイズ率：１．０〜１．３）にスプレー塗布した塗膜を室温で２４時間乾燥させたサンプルを日本電色工業株式会社製の濁度計により測定することができる。The antibacterial agent composition of the present invention is a film having a thickness of 20 to 300 nm formed by spray coating on a vinyl chloride substrate, and the haze ratio after 24 hours from coating is 5.0 or less, preferably 3.0 or less. Preferably it is 2.0 or less.
The haze ratio was determined by drying a coating film sprayed on a transparent vinyl chloride plate having a thickness of 0.5 mm (manufactured by Acrysanday, transparent hard vinyl chloride plate, haze ratio: 1.0 to 1.3) at room temperature for 24 hours. The sample thus obtained can be measured with a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd.
本発明の抗菌剤組成物中の有機ポリマーの含有割合としては、所望の透明性及び性能が得られる限り特に制限されるものではないが、抗菌剤組成物全量に対して、好ましくは１〜１０質量％、より好ましくは、１．２〜５質量％である。 The content ratio of the organic polymer in the antibacterial agent composition of the present invention is not particularly limited as long as desired transparency and performance can be obtained, but preferably 1 to 10 with respect to the total amount of the antibacterial agent composition. It is 1.2 mass%, More preferably, it is 1.2-5 mass%.
本発明の抗菌剤組成物中の抗菌成分の含有割合としては、所望の抗菌性能が得られる限り特に制限されないが、抗菌剤組成物全量に対して、好ましくは０．０１〜５質量％、より好ましくは０．０５〜１質量％である。 The content ratio of the antibacterial component in the antibacterial agent composition of the present invention is not particularly limited as long as the desired antibacterial performance is obtained, but is preferably 0.01 to 5% by mass relative to the total amount of the antibacterial agent composition. Preferably it is 0.05-1 mass%.
本発明の抗菌剤組成物中の有機ポリマーと抗菌成分との配合比（質量比）は、所望の抗菌性能が得られる限り特に制限されないが、好ましくは、抗菌成分１に対して有機ポリマーが１〜５０、より好ましくは１０〜２０である。 The blending ratio (mass ratio) of the organic polymer and the antibacterial component in the antibacterial agent composition of the present invention is not particularly limited as long as the desired antibacterial performance can be obtained. -50, more preferably 10-20.
また、本発明の抗菌剤組成物は、ｐＨを調整することによって薬液や塗膜の光安定性を高め、黄変を防ぐことができる。この際のｐＨは６．５以上、好ましくは６．５〜９、さらに好ましくは７〜９である。
ｐＨの調整は任意のｐＨ調整剤を添加することにより行うことができる。アルカリ性物質としては、通常のｐＨ調整剤に用いられる、水酸化ナトリウム、水酸化カリウム、トリエタノールアミン、炭酸ナトリウム、炭酸カリウム、燐酸ナトリウム、クエン酸ナトリウム等の水溶液を使用することができる。Moreover, the antibacterial agent composition of this invention can improve the photostability of a chemical | medical solution and a coating film by adjusting pH, and can prevent yellowing. The pH at this time is 6.5 or more, preferably 6.5 to 9, and more preferably 7 to 9.
The pH can be adjusted by adding an arbitrary pH adjusting agent. As the alkaline substance, an aqueous solution such as sodium hydroxide, potassium hydroxide, triethanolamine, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate and the like, which are used for usual pH adjusters, can be used.
（任意成分）
本発明の抗菌剤組成物は、疎水性部位を有する有機ポリマー、抗菌成分、水及びアルコール系溶媒以外に、任意の成分を含んでいてもよい。そのような任意成分としては、例えば界面活性剤、水溶性高分子化合物、レベリング剤、消泡剤、撥水成分等を例示することができる。界面活性剤は、抗菌剤組成物をより均一に溶解・分散させることができ、透明性の持続性及び抗菌効果の持続性に資する。水溶性高分子化合物は、抗菌成分等を浴室内面の天井及び壁面に所定の期間にわたり安定的に展着・保持させることができる。レベリング剤は、塗膜の表面張力を均一化し、浮まだらやハジキを防止して被塗物への濡れ性を向上させることができる。また、消泡剤は、塗膜表面の泡残りを防止することができる。(Optional component)
The antibacterial agent composition of the present invention may contain an optional component in addition to the organic polymer having a hydrophobic site, the antibacterial component, water and an alcohol solvent. Examples of such optional components include surfactants, water-soluble polymer compounds, leveling agents, antifoaming agents, and water repellent components. The surfactant can dissolve and disperse the antibacterial agent composition more uniformly, contributing to the persistence of transparency and the sustainability of the antibacterial effect. The water-soluble polymer compound can stably spread and hold an antibacterial component or the like on the ceiling and wall surface of the bathroom inner surface over a predetermined period. The leveling agent can make the surface tension of the coating film uniform, prevent floating and repellency, and improve the wettability to an object. Further, the antifoaming agent can prevent foam residue on the surface of the coating film.
界面活性剤としては、非イオン系界面活性剤等の界面活性剤を挙げることができる。非イオン系界面活性剤としては、アルキロールアマイド型；ペグノールＬ−４、ペグノールＴＨ−８、ペグノールＬ−９Ａ、ペグノールＬ−１２Ｓ、ペグノールＬ−２０Ｓ、ペグノールＴ−６、ペグノールＴＥ−１０Ａ、ペグノールＳＴ−７、ペグノールＳＴ−９、ペグノールＳＴ−１２、ペグノールＯ−６Ａ、ペグノールＯ−１０７、ペグノールＯ−１６Ａ、ペグノールＯ−２０、ペグノールＯ−２４、ペグノールＣ−１８、ペグノールＳ−４Ｄ、ペグノールＨＣ−１０（東邦化学工業株式会社製）、エマルゲン７０５、エマルゲン７０７、エマルゲン７０９（花王株式会社製）等のポリオキシエチレンアルキルエーテル型；ポリエチレングリコール脂肪酸エステル型；グリセリンエステル型；Ｐ.Ｏ.Ｅソルビット脂肪酸エステル型；ソルビタン脂肪酸エステル型；ポリオキシエチレンソルビタン脂肪酸エステル型；ペポールＡ−０６３８、ペポールＢ−１８１、ペポールＢ−１８２、ペポールＢ−１８４、ペポールＢ−１８８、ペポールＢＥＰ−０１１５（東邦化学工業株式会社製）等のポリオキシエチレンポリオキシプロピレンアルキルエーテル型；ＮＩＫＫＯＬ ＨＣＯ−４０、ＮＩＫＫＯＬ ＨＣＯ−６０、ＮＩＫＫＯＬ ＨＣＯ−１００（ニッコーケミカルズ社製）等のポリオキシエチレン硬化ヒマシ油型；ＮＩＫＫＯＬ Ｄｅｃａｇｌｙｎ １−Ｌ、ＮＩＫＫＯＬ Ｄｅｃａｇｌｙｎ １−Ｍ、ＮＩＫＫＯＬ Ｄｅｃａｇｌｙｎ １−５０ＳＶ、ＮＩＫＫＯＬ Ｈｅｘａｇｌｙｎ １−Ｌ、ＮＩＫＫＯＬ Ｈｅｘａｇｌｙｎ １−Ｍ、ＮＩＫＫＯＬ Ｈｅｘａｇｌｙｎ １−ＳＶ（ニッコーケミカルズ社製）等のポリグリセリン脂肪酸エステル型；低臭化ポリエーテル、ニューカルゲンＣＰ１２０、ＣＰ−１５−１５０、ＣＰ−１５−２００、Ｄ−９４５、Ｄ−９３５（竹本油脂株式会社製）等を挙げることができる。 Examples of the surfactant include a surfactant such as a nonionic surfactant. Nonionic surfactants include alkylol amide types; pegnol L-4, pegnol TH-8, pegnol L-9A, pegnol L-12S, pegnol L-20S, pegnol T-6, pegnol TE-10A, pegnol ST-7, pegnol ST-9, pegnol ST-12, pegnol O-6A, pegnol O-107, pegnol O-16A, pegnol O-20, pegnol O-24, pegnol C-18, pegnol S-4D, pegnol HC-10 (manufactured by Toho Chemical Co., Ltd.), Emulgen 705, Emulgen 707, Emulgen 709 (manufactured by Kao Corporation), etc .; polyoxyethylene alkyl ether type; polyethylene glycol fatty acid ester type; glycerin ester type; Sorbit fatty acid ester type; Sol Polyoxyethylene sorbitan fatty acid ester type; Pepol A-0638, Pepol B-181, Pepol B-182, Pepol B-184, Pepol B-188, Pepol BEP-0115 (manufactured by Toho Chemical Co., Ltd.) Polyoxyethylene polyoxypropylene alkyl ether type such as: NIKKOL HCO-40, NIKKOL HCO-60, NIKKOL HCO-100 (manufactured by Nikko Chemicals), etc .; 1-M, NIKKOL Decaglyn 1-50SV, NIKKOL Hexaglyn 1-L, NIKKOL Hexaglyn 1-M, NIKKOL Hexaglyn 1-SV Polyglycerin fatty acid ester type such as (Nikko Chemicals Co., Ltd.); low bromide polyether, New Calgen CP120, CP-15-150, CP-15-200, D-945, D-935 (Takemoto Yushi Co., Ltd.) Etc.
水溶性高分子化合物としては、天然水溶性高分子でも合成水溶性高分子でもあるいはこれらの混合物でもよく、上記合成水溶性高分子としては、例えばポリアクリルアミド、ポリアクリル酸、ポリメタクリル酸、ポリイタコン酸、ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、ポリビニルメチルエーテル、あるいはマレイン酸、フマル酸、クロトン酸、アニコット酸等を他のモノマーと共重合した水溶性高分子等を挙げることができ、上記天然水溶性高分子としては、例えば各種の澱粉、蛋白質、セルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等を挙げることができる。 The water-soluble polymer compound may be a natural water-soluble polymer, a synthetic water-soluble polymer, or a mixture thereof. Examples of the synthetic water-soluble polymer include polyacrylamide, polyacrylic acid, polymethacrylic acid, and polyitaconic acid. , Polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl methyl ether, or a water-soluble polymer obtained by copolymerizing maleic acid, fumaric acid, crotonic acid, anicotic acid and the like with other monomers. Examples of the polymer include various starches, proteins, cellulose, hydroxypropylcellulose, carboxymethylcellulose and the like.
レベリング剤としてはニューカルゲンＤ−１４２０、ニューカルゲンＡ−２８−Ｂ（いずれも竹本油脂株式会社製）、消泡剤としてはニューカルゲン１０２８ＰＢ、パイオニンＫ−１７（いずれも竹本油脂株式会社製）等の公知の剤を使用することができる。 As the leveling agent, New Calgen D-1420, New Calgen A-28-B (all made by Takemoto Yushi Co., Ltd.), as the antifoaming agent, New Calgen 1028PB, Pionin K-17 (all made by Takemoto Yushi Co., Ltd.), etc. These known agents can be used.
また、撥水成分としては、メガファックＦ−４７５（大日本インキ株式会社製）、メガファックＦ−４８０ＳＦ（大日本インキ株式会社製）、メガファックＦ−４７０（大日本インキ株式会社製）、メガファックＦ−４８２（大日本インキ株式会社製）等のフッ素系界面活性剤や、ディックガードＦ−９０Ｎ（大日本インキ株式会社製）、ディックガードＴＥ−５Ａ（大日本インキ株式会社製）、ディックガードＦ−４４５（大日本インキ株式会社製）等のフッ素系繊維加工剤を好適に例示することができる。また、この他に、ジメチルポリシロキサン、ジメチルシリコーンオイル、メチルハイドロジェンシリコーンオイル、変性シリコーンオイル又はそれらのエマルジョンを好適に例示することができる。 Further, as the water repellent component, MegaFuck F-475 (Dainippon Ink Co., Ltd.), MegaFuck F-480SF (Dainippon Ink Co., Ltd.), MegaFuck F-470 (Dainippon Ink Co., Ltd.), Fluorosurfactants such as MegaFuck F-482 (Dainippon Ink Co., Ltd.), Dickguard F-90N (Dainippon Ink Co., Ltd.), Dickguard TE-5A (Dainippon Ink Co., Ltd.), Fluorine-based fiber finishing agents such as Dickguard F-445 (Dainippon Ink Co., Ltd.) can be suitably exemplified. In addition, dimethylpolysiloxane, dimethyl silicone oil, methyl hydrogen silicone oil, modified silicone oil, or emulsions thereof can be preferably exemplified.
（製造方法）
本発明の抗菌剤組成物は、アルコール系溶媒を含有する場合と、アルコール系溶媒を含有しない場合で製造方法が異なる。以下に、それぞれの方法について詳細に説明する。(Production method)
The antibacterial agent composition of the present invention differs in production method between the case of containing an alcohol solvent and the case of not containing an alcohol solvent. Hereinafter, each method will be described in detail.
（１）アルコール系溶媒を含有する場合
本発明の抗菌剤組成物がアルコール系溶媒を含有する場合の製造方法は、（ａ）疎水性部位を有する有機ポリマー、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分及び組成物全体に対して２０質量％未満のアルコール系溶媒を含有する溶解液を作製する工程、及び、（ｂ）上記工程（ａ）で得た溶解液を水に分散させる工程を有する。疎水性部位を有する有機ポリマー、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分、及び、アルコール系溶媒としては前記のものを使用することができる。
工程（ａ）の溶解液にはさらに必要に応じて水、界面活性剤、レベリング剤、消泡剤等の成分を含有させることもできる。工程（ａ）において水を含有する溶解液を作製する場合、最終的な抗菌剤組成物に含有される水の５０％以下、好ましくは５〜３０％を投入することができる。
工程（ａ）の溶解液の作製には、公知の条件及び方法が使用できる。例えば攪拌混合装置を用いることができ、具体的にはマグネティックスターラー、ミキサー、ホモジナイザー、攪拌翼攪拌機等を用いることができる。(1) When containing an alcohol solvent The production method when the antibacterial agent composition of the present invention contains an alcohol solvent is as follows: (a) an organic polymer having a hydrophobic site, acid-soluble, and 20 ° C A step of preparing an antibacterial component having a solubility in 100 g of water of 0.2 g or less and a solution containing an alcohol solvent of less than 20% by mass based on the whole composition; and (b) obtained in the step (a). A step of dispersing the dissolved solution in water. As the organic polymer having a hydrophobic site, an acid-soluble antibacterial component having a solubility in 100 g of water at 20 ° C. of 0.2 g or less, and the alcohol solvent, those described above can be used.
The solution of step (a) may further contain components such as water, a surfactant, a leveling agent, and an antifoaming agent as necessary. When preparing the solution containing water in the step (a), 50% or less, preferably 5 to 30%, of water contained in the final antibacterial agent composition can be added.
Well-known conditions and methods can be used for preparation of the solution of a process (a). For example, a stirring and mixing device can be used, and specifically, a magnetic stirrer, a mixer, a homogenizer, a stirring blade stirrer, or the like can be used.
工程（ｂ）は、工程（ａ）で得られた溶解液を水に分散させる工程であるが、必要に応じて、界面活性剤、レベリング剤、消泡剤等の一部又は全部を工程（ａ）で得られた溶解液と同時に分散させてもよいし、予め水と上記剤の一部又は全部を混合した液に、工程（ａ）で得られた溶解液を分散させてもよい。
分散には公知の条件及び方法が使用でき、具体的には工程（ａ）で挙げたものと同様のものを使用することができ、水を攪拌下に、工程（ａ）で得た溶解液を水に添加して分散させる方法が好ましい。The step (b) is a step of dispersing the solution obtained in the step (a) in water. If necessary, a part or all of a surfactant, a leveling agent, an antifoaming agent, etc. may be added to the step ( The solution obtained in a) may be dispersed simultaneously with the solution obtained in step a), or the solution obtained in step (a) may be dispersed in a solution obtained by previously mixing a part or all of water and the above agent.
Known conditions and methods can be used for dispersion. Specifically, the same ones as those mentioned in step (a) can be used, and the solution obtained in step (a) while stirring water. A method in which is added to water and dispersed is preferred.
（２）アルコール系溶媒を含有しない場合
本発明の抗菌剤組成物がアルコール系溶媒を含有しない場合の製造方法は、酸可溶性で、かつ、２０℃の水１００ｇに対する溶解度が０．２ｇ以下である抗菌成分を含有するｐＨ６以下の水溶液（Ａ）と、アルカリ可溶性で、かつ、疎水性部位を有する有機ポリマーを含有するｐＨ７以上の水溶液（Ｂ）とを混合することを特徴とする。(2) When not containing alcohol solvent The production method when the antibacterial agent composition of the present invention does not contain an alcohol solvent is acid-soluble and has a solubility in 100 g of water at 20 ° C. of 0.2 g or less. An aqueous solution (A) having a pH of 6 or less containing an antibacterial component is mixed with an aqueous solution (B) having a pH of 7 or more containing an organic polymer that is alkali-soluble and has a hydrophobic site.
（２−１）水溶液（Ａ）の調製
上記抗菌成分と酸性化合物を混合して、抗菌成分が溶解したｐＨ６以下の、好ましくはｐＨ４以下の水溶液（Ａ）を調製する。
得られた水溶液（Ａ）中の抗菌成分の含有量は、抗菌成分が溶解する限り特に制限はないが、通常、０．０１〜２０質量％未満、好ましくは０．０１〜５質量％、更に好ましくは０．０１〜１質量％である。
混合は公知の手法により行うことができ、通常加温して混合するが、酸の濃度が高い場合は加温は不要である。
使用することができる酸は、塩酸、硫酸、硝酸、リン酸、ホウ酸等の無機酸、マレイン酸、シュウ酸、クエン酸、リンゴ酸等の有機酸、酸性イオン交換樹脂が挙げられ、抗菌成分の種類により、使用する酸の種類及び濃度を適宜選択しうる。(2-1) Preparation of aqueous solution (A) The above antibacterial component and acidic compound are mixed to prepare an aqueous solution (A) having a pH of 6 or less, preferably 4 or less, in which the antibacterial component is dissolved.
The content of the antibacterial component in the obtained aqueous solution (A) is not particularly limited as long as the antibacterial component is dissolved, but is usually 0.01 to less than 20% by mass, preferably 0.01 to 5% by mass, and further Preferably it is 0.01-1 mass%.
Mixing can be performed by a known method, and is usually heated and mixed, but heating is not necessary when the acid concentration is high.
Acids that can be used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid, organic acids such as maleic acid, oxalic acid, citric acid and malic acid, acidic ion exchange resins, and antibacterial components Depending on the type, the type and concentration of the acid to be used can be appropriately selected.
（２−２）水溶液（Ｂ）の調製
上記有機ポリマーとアルカリ水溶液を混合して、有機ポリマーが溶解したｐＨ７以上の水溶液（Ｂ）を調製する。
得られた水溶液（Ｂ）中の有機ポリマーの含有量は、有機ポリマーが溶解する限り特に制限はないが、通常、１〜５０質量％、好ましくは５〜２０質量％である。
混合は公知の手法により行うことができ、通常加温して混合するが、アルカリの濃度が高い場合は加温は不要である。
使用することができるアルカリは、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属水酸化物；アンモニア、トリエタノールアミン、炭酸ナトリウム、炭酸カリウム、燐酸ナトリウム、クエン酸ナトリウム、塩基性イオン交換樹脂等が挙げられ、有機ポリマーの種類により、使用するアルカリの種類及び濃度を適宜選択すればよい。(2-2) Preparation of aqueous solution (B) The organic polymer and the aqueous alkaline solution are mixed to prepare an aqueous solution (B) having a pH of 7 or more in which the organic polymer is dissolved.
Although there is no restriction | limiting in particular as long as an organic polymer melt | dissolves, content of the organic polymer in the obtained aqueous solution (B) is 1-50 mass% normally, Preferably it is 5-20 mass%.
Mixing can be performed by a known method, and is usually heated and mixed. However, heating is not necessary when the alkali concentration is high.
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; ammonia, triethanolamine, sodium carbonate, carbonate Examples thereof include potassium, sodium phosphate, sodium citrate, basic ion exchange resin, and the like, and the type and concentration of the alkali to be used may be appropriately selected depending on the type of the organic polymer.
（２−３）抗菌剤組成物の調製
本方法によって製造される抗菌剤組成物は、上記水溶液（Ａ）と上記水溶液（Ｂ）とを混合することにより製造することができる。また、必要に応じて、混合時にｐＨを調整するため、酸又はアルカリを添加してもよい。さらに、必要に応じて、各種溶剤、添加剤を加えてもよい。
本発明の抗菌剤組成物のｐＨは、抗菌成分や有機ポリマーが溶解して透明である限り、特に制限はない。
混合方法としては、通常、水溶液（Ｂ）に水溶液（Ａ）を添加して攪拌する方法で行うことが良く、特に、水溶液（Ｂ）に水溶液（Ａ）を連続的又は非連続的に滴下しながら攪拌して行うのが好ましい。
ここで、「連続的に滴下」とは、間断なく滴下することを意味し、「非連続的に滴下」とは、時間を置いて滴下することを意味する。
混合時の温度は、特に制限はないが、成分の析出を防ぐために室温以上が好ましい。
攪拌手段としては、例えば、槽内で撹拌機、マグネティックスターラー、ミキサー、ホモジナイザー、ホモディスパー等で撹拌しても良く、ラインミキサーで配管内で混合する方法等を用いることができる。
酸やアルカリは、通常、水溶液として使用するため特別の処理は必要ではないが、酸性イオン交換樹脂や塩基性イオン交換樹脂を使用する場合は、濾過等によりイオン交換樹脂を取り除くことができる。
水溶液（Ａ）と水溶液（Ｂ）を混合した時に生じる塩に関しては、必要に応じて、透析、イオン交換樹脂等により除去しても良い。(2-3) Preparation of antibacterial agent composition The antibacterial agent composition produced by this method can be produced by mixing the aqueous solution (A) and the aqueous solution (B). Moreover, in order to adjust pH at the time of mixing, you may add an acid or an alkali as needed. Furthermore, you may add various solvents and additives as needed.
The pH of the antibacterial agent composition of the present invention is not particularly limited as long as the antibacterial component and the organic polymer are dissolved and transparent.
The mixing method is usually carried out by adding the aqueous solution (A) to the aqueous solution (B) and stirring. In particular, the aqueous solution (A) is dropped continuously or discontinuously into the aqueous solution (B). It is preferable to stir with stirring.
Here, “continuous dripping” means dripping without interruption, and “non-continuous dripping” means dripping at intervals.
The temperature at the time of mixing is not particularly limited, but is preferably room temperature or higher in order to prevent precipitation of components.
As a stirring means, for example, a stirrer, a magnetic stirrer, a mixer, a homogenizer, a homodisper or the like may be stirred in the tank, and a method of mixing in a pipe with a line mixer may be used.
Since acid and alkali are usually used as an aqueous solution, no special treatment is required. However, when an acidic ion exchange resin or a basic ion exchange resin is used, the ion exchange resin can be removed by filtration or the like.
The salt produced when the aqueous solution (A) and the aqueous solution (B) are mixed may be removed by dialysis, ion exchange resin, or the like, if necessary.
（使用方法）
本発明の抗菌剤組成物を使用して菌発生を防止する方法としては、本発明の抗菌剤組成物を、窓のゴムパッキン；浴室内の天井、壁面、排水口付近、タイルの目地；洗面台；等のカビ等の生え易い箇所に塗布する方法であれば特に制限されない。
本発明の抗菌剤組成物は、防カビ剤を有効成分とする組成物の場合には、窓のゴムパッキン；浴室の天井、壁面、排水口付近、タイルの目地；洗面台等のカビの生えやすい箇所に塗布して、カビの発生を防止する目的で使用される。抗細菌又は抗酵母剤を有効成分とする組成物の場合には、トイレの床や壁、便器の内壁面や外壁面に塗布して、飛散した尿が腐敗して悪臭を発生することを防止したり、あるいは、生ごみの集積場所の周辺の床に塗布して、生ごみから流出する液体が腐敗し悪臭を発生することを防止する等、細菌、酵母の繁殖による臭気や不衛生状態を防止する目的で使用される。
塗布方法としては、具体的には、スプレー吹き付け法、エアゾール吹き付け法、バーコーター法、メイヤーバー法、刷毛塗装方法、ローラー塗装方法等を例示することができるが、スプレー吹き付け法が好ましい。抗菌剤組成物の塗布量及び抗菌剤組成物により形成される被膜の厚さは特に制限されないが、好ましくは被膜厚を５〜５００ｎｍの範囲内、より好ましくは２０〜３００ｎｍの範囲内とすることができる。(how to use)
The antibacterial agent composition of the present invention can be used to prevent the occurrence of fungi by using the antibacterial agent composition of the present invention as a rubber packing for windows; ceilings in the bathroom, wall surfaces, drain outlets, tile joints; There is no particular limitation as long as it is a method of applying to a place where mold or the like is likely to grow.
When the antibacterial agent composition of the present invention is a composition containing an antifungal agent as an active ingredient, the rubber packing of the window; the ceiling of the bathroom, the wall surface, the vicinity of the drain, the joint of the tile; It is used for the purpose of preventing the occurrence of mold by applying to easy-to-use areas. In the case of a composition containing an antibacterial or anti-yeast agent as an active ingredient, it is applied to the toilet floor and walls and the inner and outer wall surfaces of the toilet to prevent the scattered urine from decaying and generating odors. Or, it can be applied to the floor around the garbage collection area to prevent the liquid flowing out from the garbage from decaying and generating bad odors. Used for the purpose.
Specific examples of the application method include a spray spraying method, an aerosol spraying method, a bar coater method, a Mayer bar method, a brush coating method, a roller coating method, and the like, but the spray spraying method is preferable. The coating amount of the antibacterial agent composition and the thickness of the film formed by the antibacterial agent composition are not particularly limited, but preferably the film thickness is in the range of 5 to 500 nm, more preferably in the range of 20 to 300 nm. Can do.
スプレー型抗菌剤は、本発明の抗菌剤組成物が容器に収容されてなるものであれば特に制限されず、該容器としては内容物をスプレーしうる容器であれば特に制限されない。大面積を塗布する際には、スプレー回数増加による作業者への負荷が大きくなるためスポンジや塗布面との間に微小かつ均一な隙間を形成するヘラ等で塗り広げたり、スポンジに薬剤を染み込ませて使用することもできる。
スポンジ等で塗り広げる場合は、薬剤中の揮発成分が揮発する前に行うのが好ましい。揮発成分が揮発した後に塗り広げても、不均一な膜になり、抗菌効果が低下する部位が発生しやすくなる。
本発明の抗菌剤組成物は、組成物全体に対して０〜２０質量％未満のアルコール系溶媒を含むため、適度な速さで揮発成分が揮発することから、塗り広げが容易である。しかし、アルコール系溶媒が２０質量％以上含有すると、揮発が速く、塗り広げに不向きとなる。The spray-type antibacterial agent is not particularly limited as long as the antibacterial agent composition of the present invention is contained in a container, and the container is not particularly limited as long as the container can spray the contents. When a large area is applied, the load on the operator increases due to the increase in the number of sprays. Therefore, the sponge or a spatula that forms a fine and uniform gap between the application surface and the sponge is soaked in the drug. It can also be used.
When spreading with a sponge or the like, it is preferably performed before the volatile component in the drug volatilizes. Even if the volatile components are volatilized and spread, a non-uniform film is formed, and a site where the antibacterial effect is reduced tends to occur.
Since the antibacterial agent composition of the present invention contains 0 to less than 20% by mass of an alcohol-based solvent with respect to the entire composition, the volatile components volatilize at an appropriate speed, and therefore can be spread easily. However, when the alcohol solvent is contained in an amount of 20% by mass or more, the volatilization is fast and unsuitable for spreading.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
（１）アルコール系溶媒を含有する場合
［抗菌剤組成物］
第１表に示す組成の、実施例１〜２の抗菌剤組成物を調製した。
各抗菌剤組成物は、エタノール１００質量部に水３０質量部、第１表に記載の樹脂、抗菌成分、界面活性剤を溶解させた。これを室温下マグネティックスターラーで攪拌しながら所定量より３０質量部少ない水へゆっくりと滴下することで製造した。(1) When containing an alcohol solvent [antibacterial agent composition]
Antibacterial compositions of Examples 1 and 2 having the compositions shown in Table 1 were prepared.
Each antibacterial composition was prepared by dissolving 30 parts by mass of water in 100 parts by mass of ethanol and the resin, antibacterial component, and surfactant described in Table 1. This was produced by slowly dropping it into 30 parts by mass less than a predetermined amount while stirring with a magnetic stirrer at room temperature.
第１表中、樹脂ａはスチレンマレイン酸共重合体樹脂｛数平均分子量７２００、共重合比２．２：１（スチレン：マレイン酸、モル比）｝、樹脂ｂはスチレンマレイン酸樹脂｛数平均分子量６０，１００、共重合比１．０：１（スチレン：マレイン酸、モル比）｝である。
界面活性剤ＡはニューカルゲンＣＰ−１２０（竹本油脂社製）、界面活性剤ＢはニューカルゲンＣＰ−１５−２００（竹本油脂社製）である。In Table 1, resin a is a styrene maleic acid copolymer resin {number average molecular weight 7200, copolymerization ratio 2.2: 1 (styrene: maleic acid, molar ratio)}, and resin b is a styrene maleic acid resin {number average. The molecular weight is 60,100, and the copolymerization ratio is 1.0: 1 (styrene: maleic acid, molar ratio)}.
Surfactant A is New Calgen CP-120 (manufactured by Takemoto Yushi Co., Ltd.), and Surfactant B is New Calgen CP-15-200 (manufactured by Takemoto Yushi Co., Ltd.).
［試験例１］保存安定性
抗菌剤組成物調製直後の安定性を評価した。抗菌剤組成物調製時の攪拌停止１時間後に溶液状態を目視により観察した。下記基準により評価した。
○：透明液、△：やや濁り有り、×：白濁し沈降成分生成
抗菌剤組成物調製直後の安定性評価において、白濁及び沈降成分生成のなかったものについて、バイアル瓶に５質量部を計り取り保存安定性試験を実施した。試験条件及び評価基準は次のとおりである。
試験条件：０℃（１ヶ月）、室温（１ヶ月）、４０℃（１ヶ月）
評価基準：○：透明液、△：やや濁り有り、×：白濁し沈降成分生成[Test Example 1] Storage stability Stability immediately after preparation of the antibacterial agent composition was evaluated. The solution state was visually observed 1 hour after stirring was stopped when the antibacterial agent composition was prepared. Evaluation was made according to the following criteria.
○: Clear liquid, △: Slightly turbid, ×: Cloudy and sedimentation component generation In the stability evaluation immediately after preparation of the antibacterial agent composition, 5 parts by mass were measured in a vial with no cloudiness or sedimentation component generation A storage stability test was performed. The test conditions and evaluation criteria are as follows.
Test conditions: 0 ° C. (1 month), room temperature (1 month), 40 ° C. (1 month)
Evaluation criteria: ○: Clear liquid, △: Slightly turbid, ×: Cloudy and sedimentation component generation
［試験例２］スプレー塗布時の防カビ性能評価
抗菌剤組成物調製直後の安定性評価において白濁及び沈降成分生成のなかったものについて、塩ビ基板へスプレー塗布し室温で２４時間乾燥させた。塗布量は２０ｇ／ｍ２とした。それぞれの塗膜を４ｃｍ×７．５ｃｍへ裁断し、所定時間イオン交換水（５０ｍＬ）へ浸漬させ乾燥後の防カビ性能を評価した。防カビ性能評価はポテトデキストロース寒天培地上に４ｃｍ×４ｃｍの試験片を静置し、黒麹カビ胞子と液体培地の混合液を塗布し、２５℃で１週間培養したもののカビの発生状況を目視により判断した。カビ発生無しのものを−（マイナス）、カビ発生のみられたものを＋（プラス）とした。[Test Example 2] Evaluation of fungicidal performance during spray application In the stability evaluation immediately after preparation of the antibacterial agent composition, those that were not cloudy and did not generate sediment components were spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m 2 . Each coating film was cut into 4 cm × 7.5 cm and immersed in ion exchange water (50 mL) for a predetermined time to evaluate the anti-mold performance after drying. The antifungal performance was evaluated by placing a 4cm x 4cm test piece on a potato dextrose agar medium, applying a mixture of black mold mold spores and liquid medium, and culturing at 25 ° C for 1 week. Judged by. Those with no mold occurrence were marked with-(minus), and those with mold occurrence were marked with + (plus).
［試験例３］透明性評価
抗菌剤組成物調製直後の安定性評価において白濁及び沈降成分生成のなかったものについて、塩ビ基板へスプレー塗布し室温で２４時間乾燥させた。塗布量は２０ｇ／ｍ２とした。それぞれの塗膜の透明性を目視により評価した。透明のものを○、白化したものを×とした。[Test Example 3] Transparency Evaluation In the stability evaluation immediately after the preparation of the antibacterial agent composition, those that were not cloudy and did not generate sediment components were spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m 2 . The transparency of each coating film was visually evaluated. The transparent one was marked with ◯, and the whitened one was marked with ×.
［試験例４］エタノール臭気評価
抗菌剤組成物調製直後の安定性評価において白濁及び沈降成分生成のなかったものについて、塩ビ基板へスプレー塗布し室温で２４時間乾燥させた。塗布量は２０ｇ／ｍ２とした。スプレー塗布作業時のエタノール臭気を評価した。作業時、臭気がほとんど気にならないものを◎、やや臭気があるが気にならないものを○、臭気が強いものを×とした。[Test Example 4] Evaluation of ethanol odor For those having no cloudiness and no sediment component in the stability evaluation immediately after the preparation of the antibacterial agent composition, it was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 20 g / m 2 . The ethanol odor during the spray application operation was evaluated. During work, ◎ indicates that there is little odor, ◯ indicates that there is a slight odor but does not bother, and × indicates that the odor is strong.
［試験例５］エタノール着火性評価
各抗菌剤組成物を炎に向けてスプレーした際の着火性について評価した。１プッシュにつき約１ｇ噴射するスプレーボトルを使用し、火の点いているガスコンロに対して２０ｃｍの距離から１プッシュし炎の変化を目視により観察して下記基準により評価した。着火しないものを○、炎が大きくなったものを×とした。[Test Example 5] Evaluation of ethanol ignitability The ignitability when each antibacterial agent composition was sprayed toward a flame was evaluated. A spray bottle that injects about 1 g per push was used. One push was performed from a distance of 20 cm to a gas stove that was lit, and the change in flame was visually observed and evaluated according to the following criteria. The one that did not ignite was marked with ○, and the one with a large flame was marked with ×.
［試験例６］薬液への着火性評価
ガラスシャーレに抗菌剤組成物５ｍＬをいれ、炎を近づけて着火試験をおこなった。着火しないものを○、着火し、燃えたものを×とした。[Test Example 6] Evaluation of ignitability to chemical solution 5 mL of the antibacterial agent composition was placed in a glass petri dish, and an ignition test was conducted by bringing the flame closer. Those that did not ignite were marked with ○, those that ignited and burned were marked with ×.
試験例１〜６の結果をまとめて第２表に示す。 The results of Test Examples 1 to 6 are summarized in Table 2.
（２）アルコール系溶媒を含有しない場合
［実施例３〜１０］
１）チアベンダゾール（ＴＢＺ）水溶液の調製
ビーカーに０．０２５Ｎ塩酸９９．６質量部を入れ、ＴＢＺ０．４質量部を添加して０．４質量％のＴＢＺ水溶液（ｐＨ２．５）を調製し、４５℃で３０分置いた。
２）スチレンマレイン酸共重合体樹脂（ＳＭＡ）Ｎａ塩水溶液の調製
５００ｍＬナスフラスコ中に、市販の３種のスチレン無水マレイン酸樹脂２０質量部をそれぞれアセトン２００ｍＬに溶解させ、該溶液中に、室温で１Ｎ水酸化ナトリウム水溶液４００ｍＬを１時間かけて滴下した。その後１時間加熱環流を行い、放冷後２Ｎ塩酸をｐＨが３になるまで加え、生成した沈殿物を濾別、水洗し乾燥させることで、第３表に示す３種のスチレンマレイン酸共重合体をぞれぞれ１９質量部を得た。
生成物には未反応の無水マレイン酸部位が無いことを、１３Ｃ−ＮＭＲ、ＩＲ等により確認した。(2) When no alcohol solvent is contained [Examples 3 to 10]
1) Preparation of thiabendazole (TBZ) aqueous solution 99.6 parts by mass of 0.025N hydrochloric acid was added to a beaker, and 0.4 part by mass of TBZ was added to prepare a 0.4 mass% TBZ aqueous solution (pH 2.5). Placed at 30 ° C. for 30 minutes.
2) Preparation of Styrene Maleic Acid Copolymer Resin (SMA) Na Salt Aqueous Solution In a 500 mL eggplant flask, 20 parts by mass of three commercially available styrene maleic anhydride resins were dissolved in 200 mL of acetone. Then, 400 mL of 1N aqueous sodium hydroxide solution was added dropwise over 1 hour. The mixture was then heated to reflux for 1 hour, and after cooling, 2N hydrochloric acid was added until the pH reached 3, and the resulting precipitate was filtered off, washed with water and dried, so that the three types of styrene maleic acid co-polymers shown in Table 3 were used. In each case, 19 parts by mass were obtained.
It was confirmed by 13 C-NMR, IR and the like that the product had no unreacted maleic anhydride moiety.
ビーカーに１Ｎ水酸化ナトリウム水溶液３０ｍＬ、水６０ｍＬを入れ、上記第３表に示すＳＭＡ１０ｇを添加して３種類の１０質量％のＳＭＡ−Ｎａ塩水溶液（ｐＨ８）を調製し、６０℃で１時間置いた。 30 mL of 1N sodium hydroxide aqueous solution and 60 mL of water are put into a beaker, and 10 g of SMA shown in Table 3 above is added to prepare three types of 10 mass% SMA-Na salt aqueous solutions (pH 8), which are placed at 60 ° C. for 1 hour. It was.
３）抗菌剤組成物の調製
フラスコ中に、上記２）で調製したＳＭＡ−Ｎａ塩水溶液（第４表中の樹脂量となるよう添加）、水（ＳＭＡ−Ｎａ塩水溶液、ＴＢＺ水溶液を差し引いた水量）にマグネチックスターラーで攪拌しながら、上記１）で調製したＴＢＺ水溶液（第４表のＴＢＺ量となるよう添加）を滴下して第４表に示す抗菌剤組成物を調製した。必要に応じて１Ｎ水酸化ナトリウム水溶液、１Ｎ塩酸を使用してｐＨ調整を行った。実施例６では、これらの操作の後に所定量のエタノールを添加した。3) Preparation of antibacterial agent composition In the flask, the SMA-Na salt aqueous solution prepared in 2) above (added so as to have the resin amount in Table 4) and water (SMA-Na salt aqueous solution and TBZ aqueous solution) were subtracted. While stirring with a magnetic stirrer in the amount of water, the aqueous TBZ solution prepared in 1) above (added so as to have the amount of TBZ in Table 4) was dropped to prepare the antibacterial agent composition shown in Table 4. If necessary, pH adjustment was performed using 1N aqueous sodium hydroxide solution and 1N hydrochloric acid. In Example 6, a predetermined amount of ethanol was added after these operations.
［実施例１１］
０．１Ｎ塩酸を使用して、イマザリルの０．４質量％水溶液を調製した以外は実施例９と同様に抗菌剤組成物を調製した。
［実施例１２］
デカグリン１−Ｌ（ニッコーケミカルズ社製界面活性剤）を添加した以外は、実施例９と同様に抗菌剤組成物を調製した。
［実施例１３］
０．１Ｎ塩酸を使用して、カルベンダジンの０．４質量％水溶液を調製した以外は実施例９と同様に抗菌剤組成物を調製した。
［実施例１４］
１Ｎ塩酸を使用して、テブコナゾールの０．０６質量％水溶液を調製した以外は実施例９と同様に抗菌剤組成物を調製した。
［比較例６］
樹脂を添加しない以外は実施例９と同様に抗菌剤組成物を調製した。
［比較例７］
樹脂が疎水性部位を有しないポリアクリル酸（樹脂Ｄ）を用いた以外は、実施例９と同様に抗菌剤組成物を調製した。
［比較例８］
樹脂、ＴＢＺをそれぞれ第４表記載の配合量になるように水に直接添加し、混合攪拌して抗菌剤組成物を得た。
ＴＢＺは溶解せず、沈降成分が生成した。[Example 11]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that a 0.1% by mass aqueous solution of imazalil was prepared using 0.1N hydrochloric acid.
[Example 12]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that Decagulin 1-L (surfactant manufactured by Nikko Chemicals) was added.
[Example 13]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that a 0.1% by mass aqueous solution of carbendazine was prepared using 0.1N hydrochloric acid.
[Example 14]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that 1N hydrochloric acid was used to prepare a 0.06 mass% aqueous solution of tebuconazole.
[Comparative Example 6]
An antibacterial agent composition was prepared in the same manner as in Example 9 except that no resin was added.
[Comparative Example 7]
An antibacterial composition was prepared in the same manner as in Example 9 except that polyacrylic acid (resin D) in which the resin did not have a hydrophobic site was used.
[Comparative Example 8]
Resin and TBZ were directly added to water so as to have the blending amounts shown in Table 4, respectively, and mixed and stirred to obtain an antibacterial agent composition.
TBZ did not dissolve and a sediment component was generated.
［試験例７］スプレー時の防カビ性能評価
上記抗菌剤組成物を塩ビ基板へスプレー塗布し室温で２４時間乾燥させた。塗布量は３０ｇ／ｍ２とした。それぞれの塗膜を４ｃｍ×７．５ｃｍへ裁断し、所定時間イオン交換水（５０ｍＬ）へ浸漬させ乾燥後の防カビ性能を評価した。防カビ性能評価はポテトデキストロース寒天培地上に４ｃｍ×４ｃｍの試験片を静置し、黒麹カビ胞子と液体培地の混合液を塗布し、２５℃で１週間培養したもののカビの発生状況を目視により判断した。各浸漬時間浸漬したサンプルについてカビ発生の有無を観察し、胞子が発生しなかったものを防カビ性能が維持されたものとした。防カビ性能が維持された浸漬時間により耐水性を評価した。[Test Example 7] Evaluation of fungicidal performance during spraying The antibacterial agent composition was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 30 g / m 2 . Each coating film was cut into 4 cm × 7.5 cm and immersed in ion exchange water (50 mL) for a predetermined time to evaluate the anti-mold performance after drying. The antifungal performance was evaluated by placing a 4cm x 4cm test piece on a potato dextrose agar medium, applying a mixture of black mold mold spores and liquid medium, and culturing at 25 ° C for 1 week. Judged by. The samples immersed for each immersion time were observed for the presence or absence of mold, and those with no spores were assumed to maintain mold prevention performance. The water resistance was evaluated based on the immersion time during which the antifungal performance was maintained.
［試験例８］透明性評価
上記抗菌剤組成物を塩ビ基板へスプレー塗布し室温で２４時間乾燥させた。塗布量は３０ｇ／ｍ２とした。それぞれの塗膜の透明性を目視により評価した。透明のものを○、白化したものを×とした。[Test Example 8] Transparency evaluation The antibacterial agent composition was spray-coated on a PVC substrate and dried at room temperature for 24 hours. The coating amount was 30 g / m 2 . The transparency of each coating film was visually evaluated. The transparent one was marked with ◯, and the whitened one was marked with ×.
［試験例９］光安定性評価
上記抗菌剤組成物２ｇを直径９ｃｍのプラスチックシャーレへ入れ室温で放置し乾燥させた。これを直射日光下で蓋を開けて６ｈ放置した。放置後のシャーレを観察し、着色の無いものを◎、ごくわずかに着色が見られるものを○、黄変の見られたものを×とした。[Test Example 9] Light stability evaluation 2 g of the antibacterial agent composition was placed in a plastic petri dish having a diameter of 9 cm and allowed to stand at room temperature to dry. The lid was opened under direct sunlight and left for 6 hours. The petri dish after being allowed to stand was observed, where を was not colored, ◯ was slightly colored, and x was yellowed.
［試験例１０］保存安定性評価
上記抗菌剤組成物をサンプル瓶に入れ、所定温度での保存安定性を目視により判断した。変化が無く安定であるものを◎、わずかに析出物の観察されたものを○、沈降成分が生成したものを×とした。[Test Example 10] Storage stability evaluation The antibacterial agent composition was placed in a sample bottle, and the storage stability at a predetermined temperature was judged visually. The case where no change was observed and the case where the precipitate was observed was rated as わ ず か, the case where a slight precipitate was observed was marked as ◯, and the case where the sediment component was generated was marked as x.
［試験例１１］塗り広げ易さの評価
４５ｃｍ×３０ｃｍの塩化ビニル製基板に対して、住宅用洗剤スプレー容器（花王（株）製）を用いて一吹きし、市販のスポンジ（柔らかめ、水を吸いやすい）で塗り広げを行った。
スポンジの滑りやすさを評価し、引っ掛かりが無かったものを◎、引っ掛かりが１回のものを△、引っ掛かりが２回以上のものを×とした。
試験例７〜１１の評価結果を第５表に示す。[Test Example 11] Evaluation of easiness of spreading spread A 45 cm × 30 cm vinyl chloride substrate was blown using a residential detergent spray container (manufactured by Kao Corp.), and a commercially available sponge (softened, water) Spread easily.
The slipperiness of the sponge was evaluated. The case where there was no catch was rated as ◎, the case where the catch was once, Δ, and the case where the catch was 2 times or more as x.
The evaluation results of Test Examples 7 to 11 are shown in Table 5.
［比較例９〜１４］
第６表に示す組成の組成物を調製した。これらの組成物は、１Ｎ ＫＯＨａｑ．に５０質量％エタノール水溶液もしくはイオン交換水及びエタノールを添加し、さらにＳＭＡ及びＴＢＺを添加、混合し、３０分以上撹拌することにより調製した。
抗菌剤組成物調製直後の溶液状態を目視により観察し、下記基準によって透明性を評価した。
○：透明液
△：極微量の沈降物有り
×：沈降物有り
なお第６表中、「ＳＭＡ３０００」は上記第３表における樹脂Ｃのスチレンマレイン酸共重合体樹脂である。[Comparative Examples 9 to 14]
A composition having the composition shown in Table 6 was prepared. These compositions are 1N KOHaq. A 50 mass% ethanol aqueous solution or ion exchange water and ethanol were added to the mixture, and SMA and TBZ were further added, mixed, and stirred for 30 minutes or more.
The state of the solution immediately after preparation of the antibacterial agent composition was visually observed, and the transparency was evaluated according to the following criteria.
○: Clear liquid Δ: There is a very small amount of sediment ×: There is a sediment In Table 6, “SMA3000” is the styrene-maleic acid copolymer resin of resin C in Table 3 above.
本発明の抗菌剤組成物は、対象に塗布した場合の透明性や抗菌効果の持続性が高く、また、溶媒含量が低いため、製造時や使用時において溶剤臭が低く、安全性が高い。
また、本発明の製造法により、従来の製法に比して、抗菌成分を高濃度で含有させても透明な膜を提供することができるため、抗菌性能を高めることができる。さらに、抗菌剤組成物のｐＨを調整することによって抗菌剤組成物の黄変を防ぐこともでき、本発明を使用して塗り広げる時もその作業性は良好である。The antibacterial agent composition of the present invention has high transparency and long-lasting antibacterial effect when applied to an object, and has a low solvent content, so that the solvent odor is low during production and use, and the safety is high.
In addition, the production method of the present invention can provide a transparent film even when an antibacterial component is contained at a high concentration as compared with the conventional production method, so that the antibacterial performance can be enhanced. Furthermore, yellowing of the antibacterial agent composition can be prevented by adjusting the pH of the antibacterial agent composition, and the workability is good even when spreading using the present invention.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711195A (en) * | 1993-06-25 | 1995-01-13 | Tajima Inc | Wax |
| JPH11504629A (en) * | 1995-04-24 | 1999-04-27 | ノバファーム リサーチ （オーストラリア） プロプライアタリー リミティッド | Biocide surface film |
| JP2002369873A (en) * | 2001-06-15 | 2002-12-24 | Fumakilla Ltd | Water-soluble composition for odor elimination and/or sterilization and method of treating object using the same |
| WO2008004677A1 (en) * | 2006-07-07 | 2008-01-10 | Nippon Soda Co., Ltd. | Liquid antimicrobial composition capable of forming transparent films |
| WO2009084191A1 (en) * | 2007-12-28 | 2009-07-09 | Toto Ltd. | Composite material having gradually soluble coating film and coating composition |
| JP2010013622A (en) * | 2007-12-28 | 2010-01-21 | Toto Ltd | Spray agent |
| JP2010013621A (en) * | 2007-12-28 | 2010-01-21 | Toto Ltd | Hydrophilic coating agent |
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| JP2000044846A (en) * | 1998-05-27 | 2000-02-15 | Sumitomo Chem Co Ltd | Antimicrobial and antifungal synthetic resin plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711195A (en) * | 1993-06-25 | 1995-01-13 | Tajima Inc | Wax |
| JPH11504629A (en) * | 1995-04-24 | 1999-04-27 | ノバファーム リサーチ （オーストラリア） プロプライアタリー リミティッド | Biocide surface film |
| JP2002369873A (en) * | 2001-06-15 | 2002-12-24 | Fumakilla Ltd | Water-soluble composition for odor elimination and/or sterilization and method of treating object using the same |
| WO2008004677A1 (en) * | 2006-07-07 | 2008-01-10 | Nippon Soda Co., Ltd. | Liquid antimicrobial composition capable of forming transparent films |
| WO2009084191A1 (en) * | 2007-12-28 | 2009-07-09 | Toto Ltd. | Composite material having gradually soluble coating film and coating composition |
| JP2010013622A (en) * | 2007-12-28 | 2010-01-21 | Toto Ltd | Spray agent |
| JP2010013621A (en) * | 2007-12-28 | 2010-01-21 | Toto Ltd | Hydrophilic coating agent |
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| CN102655749A (en) | 2012-09-05 |
| JPWO2011074188A1 (en) | 2013-04-25 |
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