JP2022056305A - Urethane resin composition, laminate, and molding - Google Patents
Urethane resin composition, laminate, and molding Download PDFInfo
- Publication number
- JP2022056305A JP2022056305A JP2021002647A JP2021002647A JP2022056305A JP 2022056305 A JP2022056305 A JP 2022056305A JP 2021002647 A JP2021002647 A JP 2021002647A JP 2021002647 A JP2021002647 A JP 2021002647A JP 2022056305 A JP2022056305 A JP 2022056305A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- urethane resin
- titanium oxide
- mass
- copper
- 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.)
- Pending
Links
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 80
- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- 238000000465 moulding Methods 0.000 title abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000005749 Copper compound Substances 0.000 claims abstract description 28
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 53
- 239000010410 layer Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000012756 surface treatment agent Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 239000002335 surface treatment layer Substances 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 230000000840 anti-viral effect Effects 0.000 abstract description 41
- -1 quaternary ammonium salt compounds Chemical class 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 229920005862 polyol Polymers 0.000 description 23
- 239000002994 raw material Substances 0.000 description 21
- 239000010949 copper Substances 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 150000003077 polyols Chemical class 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 241000700605 Viruses Species 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 210000002615 epidermis Anatomy 0.000 description 14
- 239000011164 primary particle Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 210000003491 skin Anatomy 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000002779 inactivation Effects 0.000 description 8
- 239000002649 leather substitute Substances 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- 241000712431 Influenza A virus Species 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940093499 ethyl acetate Drugs 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000002155 anti-virotic effect Effects 0.000 description 2
- 239000003443 antiviral agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002458 infectious effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
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- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- LKPQGDNAWTWXPV-UHFFFAOYSA-N 1,5-diisocyanatooctane Chemical compound CCCC(N=C=O)CCCCN=C=O LKPQGDNAWTWXPV-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
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- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 1
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- ACOQOLIJGGKILA-UHFFFAOYSA-N 2-methylpentane-1,1-diol Chemical compound CCCC(C)C(O)O ACOQOLIJGGKILA-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
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- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
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- 241000588724 Escherichia coli Species 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical class N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
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- 230000001188 anti-phage Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- 229910000365 copper sulfate Inorganic materials 0.000 description 1
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- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
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- HXXRDHUDBAILGK-UHFFFAOYSA-L copper;2-hydroxyacetate Chemical compound [Cu+2].OCC([O-])=O.OCC([O-])=O HXXRDHUDBAILGK-UHFFFAOYSA-L 0.000 description 1
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- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- WGKSVGIFYJXABK-UHFFFAOYSA-L copper;decanedioate Chemical compound [Cu+2].[O-]C(=O)CCCCCCCCC([O-])=O WGKSVGIFYJXABK-UHFFFAOYSA-L 0.000 description 1
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- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- NQDSPXCXIOLFGI-UHFFFAOYSA-L copper;heptanoate Chemical compound [Cu+2].CCCCCCC([O-])=O.CCCCCCC([O-])=O NQDSPXCXIOLFGI-UHFFFAOYSA-L 0.000 description 1
- GYPBUYJSHBFNEJ-UHFFFAOYSA-L copper;hexadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GYPBUYJSHBFNEJ-UHFFFAOYSA-L 0.000 description 1
- ZCXLQZOQWCXFNN-UHFFFAOYSA-N copper;hexanedioic acid Chemical compound [Cu].OC(=O)CCCCC(O)=O ZCXLQZOQWCXFNN-UHFFFAOYSA-N 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- HZULDDWVCRWYCB-UHFFFAOYSA-L copper;nonanoate Chemical compound [Cu+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O HZULDDWVCRWYCB-UHFFFAOYSA-L 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- LMCVMQNMDSVUFJ-UHFFFAOYSA-N copper;pentanedioic acid Chemical compound [Cu].OC(=O)CCCC(O)=O LMCVMQNMDSVUFJ-UHFFFAOYSA-N 0.000 description 1
- NBPFTDFXKORRKN-UHFFFAOYSA-L copper;pentanoate Chemical compound [Cu+2].CCCCC([O-])=O.CCCCC([O-])=O NBPFTDFXKORRKN-UHFFFAOYSA-L 0.000 description 1
- GSCLWPQCXDSGBU-UHFFFAOYSA-L copper;phthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O GSCLWPQCXDSGBU-UHFFFAOYSA-L 0.000 description 1
- VNGORJHUDAPOQZ-UHFFFAOYSA-N copper;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CC(C)[O-] VNGORJHUDAPOQZ-UHFFFAOYSA-N 0.000 description 1
- PJBGIAVUDLSOKX-UHFFFAOYSA-N copper;propanedioic acid Chemical compound [Cu].OC(=O)CC(O)=O PJBGIAVUDLSOKX-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- ZISLUDLMVNEAHK-UHFFFAOYSA-L copper;terephthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 ZISLUDLMVNEAHK-UHFFFAOYSA-L 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical class O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
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- 239000002781 deodorant agent Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
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- 239000012212 insulator Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- KEMQGTRYUADPNZ-UHFFFAOYSA-M margarate Chemical compound CCCCCCCCCCCCCCCCC([O-])=O KEMQGTRYUADPNZ-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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- VVOPUZNLRVJDJQ-UHFFFAOYSA-N phthalocyanine copper Chemical compound [Cu].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 VVOPUZNLRVJDJQ-UHFFFAOYSA-N 0.000 description 1
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、可視光応答型光触媒を含有することで抗ウイルス性を付与することが可能なウレタン樹脂組成物、及び抗ウイルス性を付与された積層体、及び造形物に関する。 The present invention relates to a urethane resin composition capable of imparting antiviral properties by containing a visible light responsive photocatalyst, a laminate to which antiviral properties have been imparted, and a modeled product.
近年、新型コロナウィルスをはじめとした各種ウイルスや菌などが蔓延し、社会全体における抗菌・抗ウイルスを付加した製品需要が高まっている。これらの製品としては特に多数の人の手が触れる場所や、使用頻度が高い物品への要望が高いが、従来の設備や物品を全て抗菌・抗ウイルス作用を付与されたものに変更するのは手間やコストがかかるため、簡便な方法でこれらの特性を付与可能とする製品が求められている。 In recent years, various viruses and fungi such as the new coronavirus have spread, and the demand for antibacterial and antiviral products is increasing in society as a whole. As for these products, there is a high demand for places that are touched by a large number of people and articles that are frequently used, but it is not possible to change all conventional equipment and articles to those with antibacterial and antiviral effects. Since it takes time and cost, there is a demand for a product that can impart these characteristics by a simple method.
従来用いられている抗菌・抗ウイルス剤としては、各種アルコール剤、第４級アンモニウム塩化合物、銀系化合物、銅系化合物等があるが、これらは皮膚への刺激性や、経時変化による抗菌・抗ウイルス性の低減など市場の要求特性を十分に満たすことが出来ていなかった。 Conventionally used antibacterial / antiviral agents include various alcohol agents, quaternary ammonium salt compounds, silver compounds, copper compounds, etc., which are irritating to the skin and antibacterial / antiviral due to aging. It was not able to fully meet the required characteristics of the market such as reduction of antiviral properties.
これに対し、酸化チタンを用いる光触媒は人体への刺激が少なく、また長期にわたり抗菌・抗ウイルス性能が維持されるため、実用化への期待が高まっている（特許文献１参照）。 On the other hand, photocatalysts using titanium oxide are less irritating to the human body and maintain antibacterial and antiviral performance for a long period of time, so expectations for practical use are increasing (see Patent Document 1).
本発明の目的は、抗ウイルス性を付与することが可能なウレタン樹脂組成物、抗ウイルス性を付与された積層体、及び造形物を提供することである。 An object of the present invention is to provide a urethane resin composition capable of imparting antiviral properties, a laminate to which antiviral properties have been imparted, and a modeled product.
本発明は、可視光応答型光触媒を含有することで抗ウイルス性を付与することが可能なウレタン樹脂組成物、及び前記ウレタン樹脂組成物を含有することで抗ウイルス性を付与された合成皮革、及び造形物を提供する。本発明は、以下を含む。 The present invention relates to a urethane resin composition capable of imparting antiviral properties by containing a visible light responsive photocatalyst, and synthetic leather to which antiviral properties are imparted by containing the urethane resin composition. And provide shaped objects. The present invention includes:
［１］可視光応答型光触媒を含有することを特徴とするウレタン樹脂組成物。
［２］前記可視光応答型光触媒が、酸化チタン（ａ）に金属化合物が担持されたものである［１］記載のウレタン樹脂組成物。
［３］前記酸化チタン（ａ）が、ルチル型酸化チタン（ａ１）を含むものである［２］記載のウレタン樹脂組成物。
［４］前記金属化合物が、２価銅化合物である［２］又は［３］記載のウレタン樹脂組成物。
［５］前記可視光応答型光触媒の含有量は、ウレタン樹脂組成物の樹脂固形分を１００質量部とするとき０．３質量部以上６７質量部以下である［１］～［４］のいずれかに記載のウレタン樹脂組成物。
［６］繊維質基材と、前記繊維質基材の少なくとも一方の表面上に［１］～［５］のいずれかに記載のウレタン樹脂組成物により形成される表皮層と、を有する積層体。
［７］前記表皮層の表面上にさらに表面処理剤による表面処理層を有する、［６］に記載の積層体。
［８］前記繊維質基材の形態が、編物、織物、及び不織布からなる群から選択される１種である、［６］又は［７］に記載の積層体。
［９］前記［１］～［４］のいずれかに記載のウレタン樹脂組成物からなる造形物。
［１０］熱溶解積層法により造形されたことを特徴とする［９］に記載の造形物。
[1] A urethane resin composition comprising a visible light responsive photocatalyst.
[2] The urethane resin composition according to [1], wherein the visible light responsive photocatalyst is a titanium oxide (a) on which a metal compound is supported.
[3] The urethane resin composition according to [2], wherein the titanium oxide (a) contains rutile-type titanium oxide (a1).
[4] The urethane resin composition according to [2] or [3], wherein the metal compound is a divalent copper compound.
[5] Any of [1] to [4], the content of the visible light responsive photocatalyst is 0.3 parts by mass or more and 67 parts by mass or less when the resin solid content of the urethane resin composition is 100 parts by mass. The urethane resin composition described in Crab.
[6] A laminate having a fibrous base material and a skin layer formed by the urethane resin composition according to any one of [1] to [5] on at least one surface of the fibrous base material. ..
[7] The laminate according to [6], which further has a surface treatment layer with a surface treatment agent on the surface of the skin layer.
[8] The laminate according to [6] or [7], wherein the form of the fibrous base material is one selected from the group consisting of knitted fabrics, woven fabrics, and non-woven fabrics.
[9] A model made of the urethane resin composition according to any one of the above [1] to [4].
[10] The model according to [9], which is characterized by being modeled by the Fused Deposition Modeling method.
本発明におけるウレタン樹脂組成物は、抗ウイルス性を有する皮膜及び造形物を得ることができる。その皮膜を有する積層体及び造形物は、抗ウイルス性を有する。 The urethane resin composition in the present invention can obtain a film and a model having antiviral properties. The laminate and the modeled object having the film have antiviral properties.
本発明におけるウレタン樹脂組成物は、ウレタン樹脂、及び可視光応答型光触媒を含有するものである。 The urethane resin composition in the present invention contains a urethane resin and a visible light responsive photocatalyst.
前記可視光応答型光触媒としては、例えば、酸化チタン（ａ）を含む組成物が挙げられ、より一層優れた抗ウイルス性が得られる点から、酸化チタン（ａ）に金属化合物が担持されたものが好ましく挙げられる。 Examples of the visible light responsive photocatalyst include a composition containing titanium oxide (a), and a metal compound is supported on titanium oxide (a) from the viewpoint of obtaining even more excellent antiviral properties. Is preferably mentioned.
前記酸化チタン（ａ）としては、例えば、ルチル型酸化チタン（ａ１）、アナターゼ型酸化チタン、ブルッカイト型酸化チタン等を用いることができる。これらの酸化チタンは単独で用いても２種以上を併用してもよい。これらの中でも、優れた可視光領域での光触媒活性を有する点から、ルチル型酸化チタン（ａ１）を含むことが好ましい。 As the titanium oxide (a), for example, rutile-type titanium oxide (a1), anatase-type titanium oxide, brookite-type titanium oxide and the like can be used. These titanium oxides may be used alone or in combination of two or more. Among these, rutile-type titanium oxide (a1) is preferably contained because it has excellent photocatalytic activity in the visible light region.
前記ルチル型酸化チタン（ａ１）の含有率（ルチル化率）としては、より一層優れた明所及び暗所における抗ウイルス性、及び、可視光応答性が得られる点から、酸化チタン（ａ）全体に対して１５モル％以上であることが好ましく、５０モル％以上あることがより好ましく、９０モル％以上が更に好ましい。 The content of the rutile-type titanium oxide (a1) (rutileization rate) is such that titanium oxide (a) can be obtained with even better antiviral properties in bright and dark places and visible light responsiveness. It is preferably 15 mol% or more, more preferably 50 mol% or more, still more preferably 90 mol% or more based on the whole.
前記酸化チタン（ａ）の製造方法としては、一般的に、液相法と気相法とが知られている。前記液相法とは、イルメナイト鉱などの原料鉱石を溶解した液から得られる硫酸チタニルを、加水分解又は中和して酸化チタンを得る方法である。また、気相法とは、ルチル鉱などの原料鉱石を塩素化して得られる四塩化チタンと、酸素との気相反応により酸化チタンを得る方法である。なお、両方法により製造された酸化チタンを区別する方法としては、その不純物を分析することが挙げられる。前記液相法により製造された酸化チタンは、その生成物にイルメナイト鉱石中の不純物に由来するジルコニウム、ニオブなどが含まれている。これに対し、気相法では四塩化チタンを精製して、不純物を取り除く工程を有するため、酸化チタン中には、これらの不純物はほとんど含まれない。 As a method for producing the titanium oxide (a), a liquid phase method and a gas phase method are generally known. The liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which a raw material ore such as ilmenite ore is dissolved. The vapor phase method is a method for obtaining titanium oxide by a vapor phase reaction between titanium tetrachloride obtained by chlorinating a raw material ore such as rutile ore and oxygen. As a method for distinguishing titanium oxide produced by both methods, analysis of the impurities can be mentioned. The titanium oxide produced by the liquid phase method contains zirconium, niobium and the like derived from impurities in the ilmenite ore in its product. On the other hand, since the vapor phase method has a step of purifying titanium tetrachloride to remove impurities, titanium oxide hardly contains these impurities.
前記気相法により製造された酸化チタンは、均一な粒子径を生成可能な利点があるものの、２次凝集体は生成しにくいため、見かけの比表面積が高くなることにより反応工程時における混合液の粘度が高くなると考えられる。これに対し、液相法により製造された酸化チタン（ａ）は、焼成工程において緩やかな２次凝集体を生成することが考えられ、１次粒子に起因する比表面積（ＢＥＴ値）に対して、凝集力は少なく混合液の粘度を抑制することが可能である。以上の理由より、前記酸化チタン（ａ）としては、セルフクリーニング剤の生産性をより一層向上できる点から、液相法により製造された酸化チタンが好ましい。 Titanium oxide produced by the vapor phase method has the advantage of being able to generate a uniform particle size, but it is difficult to form secondary aggregates. It is considered that the viscosity of is high. On the other hand, the titanium oxide (a) produced by the liquid phase method is considered to generate loose secondary aggregates in the firing step, and has a specific surface area (BET value) due to the primary particles. The cohesive force is small and the viscosity of the mixed solution can be suppressed. For the above reasons, as the titanium oxide (a), titanium oxide produced by the liquid phase method is preferable from the viewpoint that the productivity of the self-cleaning agent can be further improved.
前記酸化チタン（ａ）のＢＥＴ比表面積としては、より一層優れた抗ウイルス性、及び、可視光応答性が得られる点から、１～２００ｍ２／ｇの範囲が好ましく、３～１００ｍ２／ｇの範囲がより好ましく、４～７０ｍ２／ｇの範囲がより好ましく、８～５０ｍ２／ｇの範囲が更に好ましく、抗ウイルス剤の生産性をより一層高めることができる点から、７．５～９．５ｍ２／ｇの範囲であることが好ましい。なお、前記ルチル型酸化チタン（ａ１）のＢＥＴ比表面積の測定方法は、後述する実施例にて記載する。 The BET specific surface area of the titanium oxide (a) is preferably in the range of 1 to 200 m 2 / g, preferably from 3 to 100 m 2 / g, from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness. The range of 7.5 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is more preferable, and the productivity of the antiviral agent can be further increased. The range is preferably 9.5 m 2 / g. The method for measuring the BET specific surface area of the rutile-type titanium oxide (a1) will be described in Examples described later.
前記酸化チタン（ａ）の１次粒子径としては、より一層優れた抗ウイルス性、及び、可視光応答性が得られる点から、０．０１～０．５μｍの範囲が好ましく、０．０６～０．３５μｍの範囲がより好ましい。なお、前記酸化チタン（ａ）の１次粒子径の測定方法は、透過型電子顕微鏡（ＴＥＭ）を使用して、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で測定した値を示す。具体的には、個々の酸化チタンの１次粒子の短軸径と長軸径を計測し、平均をその１次粒子の粒子径とし、次に１００個以上の酸化チタン粒子について、それぞれの粒子の体積（重量）を、求めた粒子径の立方体と近似して求め、体積平均粒径を平均１次粒子径とした。 The primary particle size of the titanium oxide (a) is preferably in the range of 0.01 to 0.5 μm, preferably 0.06 to 0.5 μm, from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness. A range of 0.35 μm is more preferred. The method for measuring the primary particle size of the titanium oxide (a) shows the value measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM). .. Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle diameter of the primary particle, and then each particle is obtained for 100 or more titanium oxide particles. The volume (weight) of was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size.
また、前記可視光応答型光触媒としては、可視光領域における光触媒活性を一層向上し、実用的な室内光の下で、適度な活性を発現しやすい点から、酸化チタン（ａ）に金属化合物が担持されたものを用いることが好ましい。 Further, as the visible light responsive photocatalyst, the metal compound is added to titanium oxide (a) because the photocatalytic activity in the visible light region is further improved and an appropriate activity is easily exhibited under practical indoor light. It is preferable to use a supported one.
前記金属化合物としては、例えば、銅化合物、鉄化合物、タングステン化合物等を用いることができる。これらの中でも、より一層優れた抗菌性、及び、抗ウイルス性が得られる点から、銅化合物が好ましく、２価銅化合物がより好ましい。前記酸化チタン（ａ）への金属化合物の担持方法としては、公知の手法を用いることができる。 As the metal compound, for example, a copper compound, an iron compound, a tungsten compound, or the like can be used. Among these, a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining even more excellent antibacterial and antiviral properties. As a method for supporting the metal compound on the titanium oxide (a), a known method can be used.
次に、最も好ましい態様である、酸化チタン（ａ）に２価銅化合物を担持する方法について説明する。 Next, a method of supporting the divalent copper compound on titanium oxide (a), which is the most preferable embodiment, will be described.
前記酸化チタン（ａ）に２価銅化合物を担持する方法としては、例えば、ルチル型酸化チタン（ａ１）を含む酸化チタン（ａ）、２価銅化合物原料（ｂ）、水（ｃ）、及び、アルカリ性物質（ｄ）の混合工程（ｉ）を有する方法が挙げられる。 Examples of the method for supporting the divalent copper compound on the titanium oxide (a) include titanium oxide (a) containing rutyl-type titanium oxide (a1), a raw material for the divalent copper compound (b), water (c), and water (c). , A method having a mixing step (i) of the alkaline substance (d) can be mentioned.
前記混合工程（ｉ）における前記酸化チタン（ａ）の濃度としては、３～４０質量％の範囲が好ましい。なお、本発明においては、液相法により製造された酸化チタン（ａ）を用いた場合には、酸化チタン（ａ）の濃度を高めても取扱いの良好な混合工程を行うことができ、具体的には、前記酸化チタン（ａ）の濃度が、２５質量％を超えて４０質量％以下の範囲でも良好に混合工程を行うことができる。 The concentration of the titanium oxide (a) in the mixing step (i) is preferably in the range of 3 to 40% by mass. In the present invention, when the titanium oxide (a) produced by the liquid phase method is used, a mixing step with good handling can be performed even if the concentration of the titanium oxide (a) is increased. In particular, the mixing step can be performed satisfactorily even when the concentration of the titanium oxide (a) is in the range of more than 25% by mass and 40% by mass or less.
前記２価銅化合物原料（ｂ）としては、例えば、２価銅無機化合物、２価銅有機化合物等を用いることができる。 As the divalent copper compound raw material (b), for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.
前記２価銅無機化合物としては、例えば、硫酸銅、硝酸銅、沃素酸銅、過塩素酸銅、シュウ酸銅、四ホウ酸銅、硫酸アンモニウム銅、アミド硫酸銅、塩化アンモニウム銅、ピロリン酸銅、炭酸銅等の２価銅の無機酸塩；塩化銅、フッ化銅、臭化銅等の２価銅のハロゲン化物；酸化銅、硫化銅、アズライト、マラカイト、アジ化銅などを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the divalent copper inorganic compound include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate, copper ammonium chloride, and copper pyrophosphate. Inorganic acid salts of divalent copper such as copper carbonate; halides of divalent copper such as copper chloride, copper fluoride and copper bromide; copper oxide, copper sulfide, azurite, malakite, copper azide and the like can be used. .. These compounds may be used alone or in combination of two or more.
前記２価銅有機化合物としては、例えば、蟻酸銅、酢酸銅、プロピオン酸銅、酪酸銅、吉草酸銅、カプロン酸銅、エナント酸銅、カプリル酸銅、ペラルゴン酸銅、カプリン酸銅、ミスチン酸銅、パルミチン酸銅、マルガリン酸銅、ステアリン酸銅、オレイン酸銅、乳酸銅、リンゴ酸銅、クエン酸銅、安息香酸銅、フタル酸銅、イソフタル酸銅、テレフタル酸銅、サリチル酸銅、メリト酸銅、シュウ酸銅、マロン酸銅、コハク酸銅、グルタル酸銅、アジピン酸銅、フマル酸銅、グリコール酸銅、グリセリン酸銅、グルコン酸銅、酒石酸銅、アセチルアセトン銅、エチルアセト酢酸銅、イソ吉草酸銅、β－レゾルシル酸銅、ジアセト酢酸銅、ホルミルコハク酸銅、サリチルアミン酸銅、ビス（２-エチルヘキサン酸）銅、セバシン酸銅、ナフテン酸銅、オキシン銅、アセチルアセトン銅、エチルアセト酢酸銅、トリフルオロメタンスルホン酸銅、フタロシアニン銅、銅エトキシド、銅イソプロポキシド、銅メトキシド、ジメチルジチオカルバミン酸銅等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of the divalent copper organic compound include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid. Copper, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, melitonic acid Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, acetylacetone copper, ethylacetate acetate, isokichi Copper herbate, β-resorcylate copper, diacetoacetate copper, formyl succinate copper, salicylamine acid copper, bis (2-ethylhexanoic acid) copper, sebacate copper, naphthenate copper, oxine copper, acetylacetone copper, ethylacetate acetate , Trifluoromethanesulfonate copper, phthalocyanine copper, copper ethoxydo, copper isopropoxide, copper methoxyd, copper dimethyldithiocarbamate and the like can be used. These compounds may be used alone or in combination of two or more.
前記２価銅化合物原料（ｂ）としては、前記したものの中でも、下記一般式（１）で示されるものを用いることが好ましい。
ＣｕＸ２ （１）
（式（１）において、Ｘは、ハロゲン原子、ＣＨ３ＣＯＯ、ＮＯ３、又は、（ＳＯ４）１／２を示す。）
As the divalent copper compound raw material (b), it is preferable to use the one represented by the following general formula (1) among the above-mentioned ones.
CuX 2 (1)
(In formula (1), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .)
前記式（１）におけるＸとしては、ハロゲン原子であることがより好ましく、塩素原子が更に好ましい。 The X in the formula (1) is more preferably a halogen atom, and even more preferably a chlorine atom.
前記混合工程（ｉ）における前記２価銅化合物原料（ｂ）の使用量としては、前記酸化チタン（ａ）１００質量部に対して、０．０１～２０質量部の範囲であることが好ましく、０．１～１５質量部の範囲がより好ましく、０．３～１０質量部の範囲が更に好ましい。 The amount of the divalent copper compound raw material (b) used in the mixing step (i) is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a). The range of 0.1 to 15 parts by mass is more preferable, and the range of 0.3 to 10 parts by mass is further preferable.
前記水（ｃ）は、混合工程（ｉ）における溶媒であり、水単独が好ましいが、必要に応じてその他の溶媒を含んでいてもよい。前記その他の溶媒としては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール等のアルコール溶媒；メチルエチルケトン、メチルイソブチルケトン等のケトン溶媒；ジメチルホルムアミド、テトラヒドロフラン等を用いることができる。これらの溶媒は単独で用いても２種以上を併用してもよい。 The water (c) is the solvent in the mixing step (i), and water alone is preferable, but other solvents may be contained if necessary. As the other solvent, for example, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more.
前記アルカリ性物質（ｄ）としては、例えば、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、テトラブチルアンモニウムヒドロキシド、トリエチルアミン、トリメチルアミン、アンモニア、塩基性界面活性剤等を用いることができ、水酸化ナトリウムを用いることが好ましい。 As the alkaline substance (d), for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used, and water can be used. It is preferable to use sodium oxide.
前記アルカリ性物質（ｄ）は、反応を制御しやすい点から、溶液として添加するのが好ましく、添加するアルカリ溶液の濃度としては、０．１～５ｍｏｌ／Ｌの範囲であることが好ましく、０．３～４ｍｏｌ／Ｌの範囲がより好ましく、０．５～３ｍｏｌ／Ｌの範囲が更に好ましい。 The alkaline substance (d) is preferably added as a solution from the viewpoint of easy control of the reaction, and the concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L. The range of 3 to 4 mol / L is more preferable, and the range of 0.5 to 3 mol / L is even more preferable.
前記混合工程（ｉ）は、前記酸化チタン（ａ）、２価銅化合物原料（ｂ）、水（ｃ）、及び、アルカリ性物質（ｄ）を混合すればよく、例えば、まず水（ｃ）に酸化チタン（ａ）を混合するとともに必要に応じて撹拌し、次いで、２価銅化合物原料（ｂ）を混合し、撹拌し、その後、アルカリ性物質（ｄ）を添加して撹拌する方法が挙げられる。この混合工程（ｉ）により、前記２価銅化合物原料（ｂ）由来の２価銅化合物が前記酸化チタン（ａ）に担持することとなる。 In the mixing step (i), the titanium oxide (a), the divalent copper compound raw material (b), the water (c), and the alkaline substance (d) may be mixed, for example, first in water (c). Examples thereof include a method in which titanium oxide (a) is mixed and stirred as necessary, then a divalent copper compound raw material (b) is mixed and stirred, and then an alkaline substance (d) is added and stirred. .. By this mixing step (i), the divalent copper compound derived from the divalent copper compound raw material (b) is supported on the titanium oxide (a).
前記混合工程（ｉ）における全体の撹拌時間としては、例えば、５～１２０分間が挙げられ、好ましくは１０～６０分間である。混合工程（ｉ）時における温度としては、例えば、室温～７０℃の範囲が挙げられる。 Examples of the total stirring time in the mixing step (i) include, for example, 5 to 120 minutes, preferably 10 to 60 minutes. Examples of the temperature in the mixing step (i) include a range of room temperature to 70 ° C.
酸化チタン（ａ）への２価銅化合物の担持が良好である点から、前記酸化チタン（ａ）、２価銅化合物原料（ｂ）、及び、水（ｃ）を混合・撹拌し、その後アルカリ性物質（ｄ）を混合・撹拌した後の混合物のｐＨとしては、好ましくは８～１１の範囲であり、より好ましくは９．０～１０．５の範囲である。 Since the support of the divalent copper compound on the titanium oxide (a) is good, the titanium oxide (a), the divalent copper compound raw material (b) and the water (c) are mixed and stirred, and then alkaline. The pH of the mixture after mixing and stirring the substance (d) is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.
前記混合工程（ｉ）が終了した後には、混合液を固形分として分離することができる。前記分離を行う方法としては、例えば、濾過、沈降分離、遠心分離、蒸発乾燥等が挙げられるが、濾過が好ましい。分離した固形分は、その後必要に応じて、水洗、解砕、分級等を行ってもよい。 After the mixing step (i) is completed, the mixed liquid can be separated as a solid content. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation and drying, and the like, but filtration is preferable. The separated solid content may be subsequently washed with water, crushed, classified, or the like, if necessary.
前記固形分を得た後には、前記酸化チタン（ａ）上に担持された前記２価銅化合物原料（ｂ）由来の２価銅化合物を、より強固に結合することができる点から、固形分を熱処理することが好ましい。熱処理温度としては、好ましくは１５０～６００℃の範囲であり、より好ましくは２５０～４５０℃の範囲である。また、熱処理時間は、好ましくは１～１０時間であり、より好ましくは、２～５時間である。 After obtaining the solid content, the solid content can be more firmly bonded to the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a). Is preferably heat-treated. The heat treatment temperature is preferably in the range of 150 to 600 ° C, more preferably in the range of 250 to 450 ° C. The heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
以上の方法によって、酸化チタン（ａ）に２価銅化合物が担持した酸化チタンを含有する酸化チタン組成物が得られる。前記酸化チタン（ａ）に担持された２価銅化合物の担持量としては、酸化チタン（ａ）１００質量部に対して、０．０１～２０質量部の範囲であることが、抗ウイルス性を含む光触媒活性の点から好ましい。前記２価銅化合物の担持量は、前記混合工程（ｉ）における前記２価銅化合物原料（ｂ）の使用量によって調整することができる。 By the above method, a titanium oxide composition containing titanium oxide in which a divalent copper compound is supported on titanium oxide (a) can be obtained. The amount of the divalent copper compound supported on the titanium oxide (a) is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a), which provides antiviral properties. It is preferable from the viewpoint of the photocatalytic activity including. The amount of the divalent copper compound supported can be adjusted by the amount of the divalent copper compound raw material (b) used in the mixing step (i).
ウレタン樹脂組成物における可視光応答型光触媒の含有量は本発明の効果が得られる範囲において特に制限されるものではないが、ウレタン樹脂組成物の樹脂固形分を１００質量部とするとき、下限は通常０．３質量部以上、好ましくは３．３質量部以上、より好ましくは１０質量部以上であり、上限は通常６７質量部以下、好ましくは５０質量部以下、より好ましくは３３質量部以下である。これらの上限値と下限値はいずれの組み合わせでもよい。ウレタン樹脂組成物における可視光応答型光触媒の含有量は、ウレタン樹脂組成物の樹脂固形分を１００質量部とするとき、通常０．３質量部以上６７質量部以下、好ましくは３．３質量部以上５０質量部以下、より好ましくは１０質量部以上３３質量部以下である。 The content of the visible light responsive photocatalyst in the urethane resin composition is not particularly limited as long as the effect of the present invention can be obtained, but when the resin solid content of the urethane resin composition is 100 parts by mass, the lower limit is It is usually 0.3 parts by mass or more, preferably 3.3 parts by mass or more, more preferably 10 parts by mass or more, and the upper limit is usually 67 parts by mass or less, preferably 50 parts by mass or less, more preferably 33 parts by mass or less. be. Any combination of these upper limit values and lower limit values may be used. The content of the visible light responsive photocatalyst in the urethane resin composition is usually 0.3 parts by mass or more and 67 parts by mass or less, preferably 3.3 parts by mass, when the resin solid content of the urethane resin composition is 100 parts by mass. It is 50 parts by mass or less, more preferably 10 parts by mass or more and 33 parts by mass or less.
本発明で用いられるウレタン樹脂としては、例えば、ポリエーテル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエステル系ウレタン樹脂、樹脂及びこれらの変性物等が挙げられ、熱硬化性ウレタン樹脂、熱可塑性ポリウレタン樹脂のいずれを用いることもできる。この中でも、スポーツ靴や衣料用途で、柔軟性が必要な場合、ポリエーテル系ウレタン樹脂が好適である。また、家具、車両等の用途で長期耐久性が必要な場合、ポリカーボネート系ウレタン樹脂が好適である。前記ウレタン樹脂の分子量の分子量は、用途や要求性能によって異なるが、数平均分子量で５，０００～５０，０００、好ましくは、５，０００～１５，０００の範囲で、適宜選択すれば良い。 Examples of the urethane resin used in the present invention include polyether-based urethane resins, polycarbonate-based urethane resins, polyester-based urethane resins, resins and modified products thereof, and examples thereof include thermosetting urethane resins and thermoplastic polyurethane resins. Either can be used. Among these, a polyether urethane resin is preferable when flexibility is required for sports shoes and clothing applications. Further, when long-term durability is required for applications such as furniture and vehicles, polycarbonate urethane resin is suitable. The molecular weight of the urethane resin varies depending on the intended use and required performance, but may be appropriately selected in the range of 5,000 to 50,000, preferably 5,000 to 15,000 in terms of number average molecular weight.
前記ウレタン樹脂の原料であるポリオール成分としては、例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、ポリエチレンアジペート、ポリプロピレンアジペート、ポリオキシテトラエチレンアジペート等が挙げられる。これらのポリオール成分は、単独で用いることも、２種類以上を併用して用いることもできる。 Examples of the polyol component which is a raw material of the urethane resin include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyethylene adipate, polypropylene adipate, and polyoxytetraethylene adipate. These polyol components can be used alone or in combination of two or more.
また、前記ウレタン樹脂の原料であるイソシアネート成分としては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、２，２’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、３，３’－ジメチル－４，４’－ビフェニレンジイソシアネート、３，３’－ジメトキシ－４，４’－ビフェニレンジイソシアネート、３，３’－ジクロロ－４，４’－ビフェニレンジイソシアネート、１，５－ナフタレンジイソシアネート、１，５－テトラヒドロナフタレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。これらのポリイソシアネートは、単独で用いることも、２種類以上を併用して用いることもできる。
Examples of the isocyanate component that is the raw material of the urethane resin include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylenedi isocyanate, p-phenylenedi isocyanate, and 2,2'-diphenylmethane diisocyanate. 2,4'-Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 3,3'-Dichloro-4,4'-biphenylenediocyanate, 1,5-naphthalenediocyanate, 1,5-tetrahydronaphthalenediocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and the like can be mentioned. These polyisocyanates can be used alone or in combination of two or more.
本発明のウレタン樹脂組成物には、必要に応じ、架橋剤を添加することができる。この架橋剤は、本発明で用いられるウレタン樹脂と架橋できるものであれば、特に限定されない。このような架橋剤としては、ウレタン樹脂中の活性水素原子等の官能基と反応することができる官能基を１分子中に２つ以上有する化合物、もしくは、環状化合物であって、その環が開環することにより、ウレタン樹脂中の活性水素原子等の官能基と反応して結合を形成し、ウレタン樹脂を架橋することのできる化合物が挙げられる。具体的な例としては、例えば、エポキシ化合物、アジリジン化合物、カルボジイミド化合物、ポリイソシアネート化合物、オキサゾリン化合物、メラミンホルムアミド化合物、ユリアメチロール化合物等が挙げられる。これらの中でも、ポリイソシアネート化合物が好ましい。これらの架橋剤は、単独で用いることも、２種類以上を併用して用いることもできる。 A cross-linking agent can be added to the urethane resin composition of the present invention, if necessary. The cross-linking agent is not particularly limited as long as it can cross-link with the urethane resin used in the present invention. Such a cross-linking agent is a compound having two or more functional groups in one molecule capable of reacting with a functional group such as an active hydrogen atom in a urethane resin, or a cyclic compound whose ring is opened. Examples thereof include compounds capable of cross-linking a urethane resin by reacting with a functional group such as an active hydrogen atom in the urethane resin to form a bond by ringing. Specific examples include, for example, epoxy compounds, aziridine compounds, carbodiimide compounds, polyisocyanate compounds, oxazoline compounds, melamineformamide compounds, ureamethylol compounds and the like. Among these, a polyisocyanate compound is preferable. These cross-linking agents may be used alone or in combination of two or more.
本発明のウレタン樹脂組成物には、塗布性を付与するため、有機溶剤を添加することもできる。前記有機溶剤は、前記ウレタン樹脂を溶解するものであれば、特に限定されない。このような有機溶剤としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド（以下、ＤＭＦと略す。）等の有機溶剤が挙げられる。また、樹脂溶液の塗布後の乾燥性を向上させるため、メタノール、エタノール、イソプロピルアルコール、トルエン、メチルエチルケトン、酢酸エチル、シクロヘキサノン、エチルセロソルブ、メチルセロソルブ、プロピレングリコールメチルエーテル、プロピレングリコールメチルエーテルアセテート、Ｎ－メチルピロリドン等が使用できる。これらの中でも、シクロヘキサノン、酢酸エチル、メチルエチルケトン、エタノール、メタノール、イソプロピルアルコール等の沸点が１００℃未満のものが、特に好ましい。これらの乾燥性を向上させるために用いる溶剤は、単独で用いることも、２種類以上を併用して用いることもできる。 An organic solvent may be added to the urethane resin composition of the present invention in order to impart coatability. The organic solvent is not particularly limited as long as it dissolves the urethane resin. Examples of such an organic solvent include organic solvents such as N, N-dimethylformamide (hereinafter, abbreviated as DMF). In addition, in order to improve the drying property after application of the resin solution, methanol, ethanol, isopropyl alcohol, toluene, methyl ethyl ketone, ethyl acetate, cyclohexanone, ethyl cellosolve, methyl cellosolve, propylene glycol methyl ether, propylene glycol methyl ether acetate, N- Methylpyrrolidone or the like can be used. Among these, cyclohexanone, ethyl acetate, methyl ethyl ketone, ethanol, methanol, isopropyl alcohol and the like having a boiling point of less than 100 ° C. are particularly preferable. The solvent used to improve these drying properties may be used alone or in combination of two or more.
前記有機溶剤及び必要に応じて乾燥性を向上させるために用いる溶剤の合計の配合量は、樹脂組成物の固形分濃度が５～６０質量％となる範囲が好ましい。 The total amount of the organic solvent and the solvent used to improve the drying property, if necessary, is preferably in the range of 5 to 60% by mass in the solid content concentration of the resin composition.
本発明のウレタン樹脂組成物は、繊維質基材の表皮層、接着層及び中間層の他、表皮層の表面上の表面処理層にも好適に用いることができる。 The urethane resin composition of the present invention can be suitably used not only for the skin layer, the adhesive layer and the intermediate layer of the fibrous base material, but also for the surface treatment layer on the surface of the skin layer.
本発明のウレタン樹脂組成物には、更に必要に応じて、架橋促進剤、有機顔料等の着色剤、難燃剤、酸化防止剤等の各種添加剤、ウレタン樹脂以外の樹脂等を加えることもできる。 Further, if necessary, a cross-linking accelerator, a coloring agent such as an organic pigment, various additives such as a flame retardant and an antioxidant, a resin other than the urethane resin, and the like can be added to the urethane resin composition of the present invention. ..
さらに各種造形法により造形物を製造する際には熱可塑性ウレタン樹脂を用いることが好ましい、これら熱可塑性ポリウレタンは、ポリオールと、ポリイソシアネートとを鎖伸長剤の存在下で重合することにより得られる樹脂である。 Further, it is preferable to use a thermoplastic urethane resin when producing a model by various modeling methods. These thermoplastic polyurethanes are resins obtained by polymerizing a polyol and a polyisocyanate in the presence of a chain extender. Is.
前記熱可塑性ポリウレタン樹脂の原料として用いるポリオールとしては、特に限定されず、従来公知のものを使用できる。これらポリオールとしては、例えば、ポリエステル系ポリオール、ポリエーテル系ポリオール、ポリカーボネート系ポリオール、ポリラクトン系ポリオールなどの高分子ポリオールが挙げられる。これらのポリオールは、単独で用いてもよく、２種以上を併用してもよい。 The polyol used as a raw material for the thermoplastic polyurethane resin is not particularly limited, and conventionally known ones can be used. Examples of these polyols include polymer polyols such as polyester-based polyols, polyether-based polyols, polycarbonate-based polyols, and polylactone-based polyols. These polyols may be used alone or in combination of two or more.
前記熱可塑性ポリウレタン樹脂の原料として用いるポリオールの平均分子量（数平均分子量）は、好ましくは５００～５，０００、より好ましくは７００～４，０００の範囲で、適宜選択すれば良い。 The average molecular weight (number average molecular weight) of the polyol used as a raw material for the thermoplastic polyurethane resin may be appropriately selected in the range of preferably 500 to 5,000, more preferably 700 to 4,000.
前記熱可塑性ウレタン樹脂の原料として用いるポリオールとしては、具体的には例えば、ポリテトラメチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、１，４－シクロヘキサンジメタノールなどの低分子ポリオールと、ジエチレンカーボネート、ジプロピレンカーボネート、ジフェニルカーボネートなどのカーボネート化合物との脱アルコール反応により得られるポリオール等が挙げられる。これらのポリオール成分は、単独で用いることも、２種類以上を併用して用いることもできる。 Specific examples of the polyol used as a raw material for the thermoplastic urethane resin include polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, ethylene glycol, propylene glycol, and butanediol. , Pentandiol, hexanediol, octanediol, nonanediol, 1,4-cyclohexanedimethanol and other low molecular weight polyols, and polyols obtained by dealcohol reaction with carbonate compounds such as diethylene carbonate, dipropylene carbonate and diphenyl carbonate. Can be mentioned. These polyol components can be used alone or in combination of two or more.
また、前記熱可塑性ウレタン樹脂の原料として用いるポリイソシアネートとしては、イソシアネート基を２個以上有するものであれば特に限定されず、従来公知のものを使用できる。例えば、１，６－ヘキサメチレンジイソシアネート（ＨＤＩ）、２，２，４－トリメチルヘキサメチレンジイソシアネート、メチレンジイソシアネート、イソプロピレンジイソシアネート、リジンジイソシアネート、リジンジイソシアネートメチルエステル、１，５－オクチレンジイソシアネート、等の脂肪族イソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、ノルボルネンジイソシアネート、水添トリレンジイソシアネート、メチルシクロヘキサンジイソシアネート、イソプロピリデンビス（４－シクロヘキシルイソシアネート）、ダイマー酸ジイソシアネートなどの脂環族イソシアネート、２，４－もしくは２，６－トリレンジイソシアネート（ＴＤＩ）、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、１，５－ナフチレンジイソシアネート、ｐ－もしくはｍ－キシリレンジイソシアネート（ＸＤＩ）、トリジンジイソシアネート、ｐ－フェニレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルスルホンジイソシアネート、ジアニシジンジイソシアネート、テトラメチル－ｍ－キシリレンジイソシアネート、等の芳香族イソシアネート、トリフェニルメタントリイソシアネート、トリイソシアネートフェニルチオフォスフェート、ポリメチレンポリフェニレンポリイソシアネート（ポリメリックＭＤＩ）、ＨＤＩやＴＤＩのトリマーであるイソシアヌレート変性体、ビウレット変性体等、エチレングリコール、プロピレングリコール、ブタンジオール、ペンタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、１，４－シクロヘキサンジメタノールなどの低分子ポリオールと、ジエチレンカーボネート、ジプロピレンカーボネート、ジフェニルカーボネートなどのカーボネート化合物との脱アルコール反応により得られるポリオール等が挙げられる。これらのポリイソシアネートは、単独で用いることも、２種類以上を併用して用いることもできる。 The polyisocyanate used as a raw material for the thermoplastic urethane resin is not particularly limited as long as it has two or more isocyanate groups, and conventionally known polyisocyanates can be used. For example, fats such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, lysine diisocyanate methyl ester, 1,5-octylene diisocyanate, etc. Alicyclic isocyanates such as group isocyanates, 4,4'-dicyclohexylmethane diisocyanates, isophorone diisocyanates (IPDI), norbornene diisocyanates, hydrogenated tolylene diisocyanates, methylcyclohexanediisocyanates, isopropylidenebis (4-cyclohexylisocyanates), dimerate diisocyanates. , 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, p- or m-xylylene diisocyanate (XDI), trizine diisocyanate , P-Phenylene diisocyanate, diphenyl ether diisocyanate, diphenylsulfone diisocyanate, dianisidine diisocyanate, tetramethyl-m-xylylene diisocyanate, etc. Polymeric MDI), isocyanurate modified products that are trimmers of HDI and TDI, biuret modified products, etc., ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, nonanediol, 1,4-cyclohexanedimethanol, etc. Examples thereof include polyols obtained by a dealcohol reaction between the low molecular weight polyol of No. 1 and a carbonate compound such as diethylene carbonate, dipropylene carbonate and diphenyl carbonate. These polyisocyanates can be used alone or in combination of two or more.
前記熱可塑性ウレタン樹脂の原料として用いる鎖伸長剤としては、特に限定されず、従来公知のものを使用できる。鎖伸長剤としては、例えば、従来公知の多価アルコール類やアミン類がいずれも使用できるが、炭素原子数が２～１０の低分子ポリオールが好ましい。これら低分子ポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、２－メチルペンタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、オクタンジオール、ノナンジオール、デカンジオール、トリメチールプロパン、グリセリンなどの脂肪族ポリオール、シクロヘキサンジオール、シクロヘキサンジメタノールなどの脂環族ポリオール、ビスヒドロキシエトキシベンゼン、キシレングリコールなどの芳香族ポリオール、などが挙げられる。これらの鎖伸長剤は、単独で用いることも、２種類以上を併用して用いることもできる。 The chain extender used as a raw material for the thermoplastic urethane resin is not particularly limited, and conventionally known ones can be used. As the chain extender, for example, conventionally known polyhydric alcohols and amines can be used, but a small molecule polyol having 2 to 10 carbon atoms is preferable. Examples of these low molecular weight polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpentanediol, 1,5-pentanediol, and 1, Alicyclic polyols such as 6-hexanediol, neopentyl glycol, octanediol, nonanediol, decanediol, trimetylpropane and glycerin, alicyclic polyols such as cyclohexanediol and cyclohexanedimethanol, bishydroxyethoxybenzene and xylene glycol, etc. Aromatic polyols, etc. These chain extenders can be used alone or in combination of two or more.
本発明において熱可塑性ポリウレタンを用いる場合は、必要に応じて、シランカップリング剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、可塑剤、熱安定剤、酸化防止剤、紫外線吸収剤、耐光安定剤、充填剤、繊維系補強材、顔料、蛍光増白剤、発泡剤、熱可塑性樹脂、熱硬化性樹脂、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、結晶水含有化合物、難燃剤、吸水剤、吸湿剤、消臭剤、抗菌剤、防黴剤、ブロッキング防止剤、加水分解防止剤、有機水溶性化合物、無機水溶性化合物等の添加剤を配合してもよい。 When a thermoplastic polyurethane is used in the present invention, a silane coupling agent, a filler, a thixo-imparting agent, a tackifier, a wax, a plasticizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, and a light-resistant agent are used, if necessary. Stabilizers, fillers, fiber-based reinforcements, pigments, optical brighteners, foaming agents, thermoplastic resins, thermosetting resins, dyes, conductivity-imparting agents, antistatic agents, moisture permeability improvers, water repellents, Oil repellent, hollow foam, crystalline water-containing compound, flame retardant, water absorbent, hygroscopic agent, deodorant, antibacterial agent, anti-mold agent, blocking inhibitor, hydrolysis inhibitor, organic water-soluble compound, inorganic water-soluble compound Additives such as may be blended.
次に、ウレタン樹脂組成物が使用される具体的な態様について説明する。 Next, a specific embodiment in which the urethane resin composition is used will be described.
本発明におけるウレタン樹脂組成物は、繊維質基材用のコーティング剤として用いることができる。コーティング剤とは基材の表面上に形成される皮膜を得る剤であって、表面処理剤の概念を含む。繊維質基材の表面上にウレタン樹脂組成物をコーティングすることで、抗ウイルス性に優れる表皮層を有する積層体を得ることができる。表皮層の表面上にさらにウレタン樹脂組成物を表面処理することで、繊維質基材の表面上に表皮層及び表面処理層を有する積層体を得て、抗ウイルス性をさらに向上させることができる。 The urethane resin composition in the present invention can be used as a coating agent for a fibrous substrate. The coating agent is an agent for obtaining a film formed on the surface of a base material, and includes the concept of a surface treatment agent. By coating the surface of the fibrous base material with the urethane resin composition, a laminate having a skin layer having excellent antiviral properties can be obtained. By further surface-treating the urethane resin composition on the surface of the skin layer, a laminate having the skin layer and the surface-treated layer on the surface of the fibrous base material can be obtained, and the antiviral property can be further improved. ..
繊維質基材の材質の例としては、例えばコットン（綿）、リネン（麻）、シルク（絹）等の天然繊維（植物繊維・動物繊維）；ポリエステル、ナイロン、アクリル、ポリウレタン等の化学繊維が挙げられる。 Examples of materials for fibrous base materials include natural fibers (vegetable fibers / animal fibers) such as cotton, linen (linen), and silk (silk); and chemical fibers such as polyester, nylon, acrylic, and polyurethane. Can be mentioned.
繊維質基材の形態の例としては、例えば編物、織物、不織布等が挙げられる。 Examples of the form of the fibrous base material include knitted fabrics, woven fabrics, and non-woven fabrics.
本発明における積層体を有する物品の具体例としては、例えば、合成皮革、人工皮革、天然皮革、ポリ塩化ビニル（ＰＶＣ）レザーを用いた自動車内装シート、スポーツ靴、衣料、家具、熱可塑性オレフィン（ＴＰＯ）レザー、ダッシュボード、インスツルメントパネル等が挙げられる。 Specific examples of the article having a laminate in the present invention include, for example, synthetic leather, artificial leather, natural leather, automobile interior seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, and thermoplastic olefins ( TPO) Leather, dashboard, instrument panel, etc.
本発明における積層体は、公知の乾式成膜法によって製造することができる。例えば、以下の方法が挙げられる。 The laminate in the present invention can be produced by a known dry film forming method. For example, the following method can be mentioned.
離型紙上に表皮層用樹脂組成物をドクターナイフで塗布した後、乾燥させる。次に、その表皮層の乾燥塗膜上に接着層用樹脂組成物をドクターナイフで塗布した後、予備乾燥させる。更に不織布と貼り合わせた後、乾燥させる。その後、エージングした後、離型紙を剥がすことにより、積層体が得られる。 The resin composition for the epidermis layer is applied on the release paper with a doctor knife, and then dried. Next, the resin composition for the adhesive layer is applied on the dry coating film of the skin layer with a doctor knife, and then pre-dried. Further, it is bonded to the non-woven fabric and then dried. Then, after aging, the release paper is peeled off to obtain a laminated body.
前記ウレタン樹脂組成物による層の厚さとしては、例えば、０．１～１００μｍの範囲であることが好ましい。 The thickness of the layer made of the urethane resin composition is preferably in the range of, for example, 0.1 to 100 μm.
また、本発明におけるウレタン樹脂組成物は各種造形法により造形物とすることができる。これら造形法としては熱溶解積層法等の３次元造形法、及びバキューム成形、射出成形等公知の造形法を用いることができるが、可視光応答型光触媒が造形物上に均一に配置され本発明の効果が好適に得られることから熱溶解積層法等の３次元造形法により造形することが好ましい。 Further, the urethane resin composition in the present invention can be made into a model by various modeling methods. As these modeling methods, a three-dimensional modeling method such as a fused deposition modeling method and a known modeling method such as vacuum molding or injection molding can be used, but the visible light responsive stereolithography is uniformly arranged on the modeled object and the present invention is used. It is preferable to perform molding by a three-dimensional molding method such as a hot melt lamination method because the effect of the above can be preferably obtained.
本発明の造形物を製造する際に、熱溶解積層法等の三次元造形法を選択する場合に用いるウレタン樹脂組成物の形態としては、粉体、ペレット、フィラメント等が挙げられ、使用する三次元造形装置により適宜選択すれば良い。 Examples of the form of the urethane resin composition used when selecting a three-dimensional modeling method such as the Fused Deposition Modeling method when producing the modeled product of the present invention include powders, pellets, filaments, etc., and the tertiary used. It may be appropriately selected depending on the original modeling device.
前記３次元造形法による造形物としては、例えば、ベルト、チューブ、ホース、電線被覆材、ケーブル被覆材、防ホース、ギアー、キャスター、パッキング類、風力発電用風車等の機械工業部品、バンパー、サイドモール、テールランプシール、スノーチェーン、ボールジョイントシール、等速ジョイントブーツ、ベローズ、バネカバー材、ＡＢＳケーブル、ＡＢＳケーブルプラグ、インパネ表皮、ギヤノブ、コンソールボックス、ドアシールカバー、シート材、ノブ類等の自動車部品、各種シート類、エアーマット、合成皮革、保護フィルム等のフィルム・シート、靴底、時計バンド、カメラグリップ、アニマルイヤータッグ、スマホケース、タブレットケース、キーボード保護カバー、装飾品等の日用品、心臓バルブ、バイバス装置、人工心室、透析用チューブ、薄膜、コネクター、カテーテル、医療用チューブ、ペースメーカーの絶縁体等の医療用途品、内外装材等の建築用資材、スキー板、スノーボード、サーフボード、ラケット等のスポーツ用品等を挙げられ、屋内外の幅広い分野に用いることができる。 Examples of the modeled object by the three-dimensional modeling method include belts, tubes, hoses, electric wire covering materials, cable covering materials, hose-proofing, gears, casters, packings, mechanical industrial parts such as wind turbines for wind power generation, bumpers, and sides. Auto parts such as moldings, tail lamp seals, snow chains, ball joint seals, constant velocity joint boots, bellows, spring cover materials, ABS cables, ABS cable plugs, instrument panel skins, gear knobs, console boxes, door seal covers, seat materials, knobs, etc. Various sheets, air mats, synthetic leather, film sheets such as protective films, shoe soles, watch bands, camera grips, animal ear tags, smartphone cases, tablet cases, keyboard protective covers, daily necessities such as decorations, heart valves, bypasses Equipment, artificial ventricles, dialysis tubes, thin films, connectors, catheters, medical tubes, medical products such as pacemaker insulators, building materials such as interior and exterior materials, sports equipment such as ski boards, snowboards, surfboards, and rackets. It can be used in a wide range of indoor and outdoor fields.
以下、実施例を用いて、本発明をより具体的に説明する。
［光触媒の調整例１］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法（硫酸法）
ｃ）物性値
・ＢＥＴ比表面積：９．０ｍ２／ｇ
・ルチル化率：９５．４％
・１次粒子径：０．１８μｍ
Hereinafter, the present invention will be described in more detail with reference to Examples.
[Photocatalyst adjustment example 1]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method)
c) Physical properties / BET specific surface area: 9.0 m 2 / g
-Rutilation rate: 95.4%
-Primary particle diameter: 0.18 μm
［酸化チタン（ａ）のＢＥＴ比表面積の測定方法］
株式会社マウンテック製全自動ＢＥＴ比表面積測定装置「ＭａｃＳＯＲＢ ＨＭ ｍｏｄｅｌ－１２０８」を使用して、比表面積測定（ＢＥＴ１点法）による測定を行った。
[Measuring method of BET specific surface area of titanium oxide (a)]
The measurement was performed by the specific surface area measurement (BET 1-point method) using the fully automatic BET specific surface area measuring device "MacSORB HM model-1208" manufactured by Mountech Co., Ltd.
［酸化チタン（ａ）のルチル化率の測定方法］
島津製作所株式会社製Ｘ線回折装置「ＸＲＤ－６１００」を使用して、ルチル型結晶に対応するピーク高さ割合を酸化チタン全体の結晶（ルチル型、ブルッカイト型、アナターゼ型）に対応するピーク高さから算出した。
[Measurement method of rutileization rate of titanium oxide (a)]
Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile type crystal is set to the peak height corresponding to the crystal of the whole titanium oxide (rutile type, brookite type, anatase type). Calculated from the above.
［酸化チタン（ａ）の１次粒子径の測定方法］
透過型電子顕微鏡（ＴＥＭ）を使用して、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で測定した。具体的には、個々の酸化チタンの１次粒子の短軸径と長軸径を計測し、平均をその１次粒子の粒子径とし、次に１００個以上の酸化チタン粒子について、それぞれの粒子の体積（重量）を、求めた粒子径の立方体と近似して求め、体積平均粒径を平均１次粒子径とした。
[Measuring method of primary particle size of titanium oxide (a)]
A transmission electron microscope (TEM) was used to measure the size of the primary particles directly from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle diameter of the primary particle, and then each particle is obtained for 100 or more titanium oxide particles. The volume (weight) of was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size.
（２）製造工程
ａ）混合工程（反応工程）
前記酸化チタン６００質量部、塩化銅（ｉｉ）二水和物８質量部、水９００質量部をステンレス容器中に混合した。次いで、混合物を撹拌機（特殊機化工業株式会社製「ロボミクス」）で撹拌し、１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を混合液のｐＨが１０になるまで滴下した。
ｂ）脱水工程
定性濾紙（５Ｃ）により減圧濾過をおこない、混合液から固形分を分離し、更にイオン交換水で洗浄を実施した。次いで、洗浄後の固形物を１２０℃で１２時間乾燥し、水分を除去した。乾燥後、ミル（イワタニ産業株式会社製「ミルサー」）で粉状の酸化チタン組成物を得た。
ｃ）熱処理工程
精密恒温器（ヤマト科学株式会社製「ＤＨ６５０」）を用いて酸素存在下で４５０℃、３時間熱処理し、２価銅化合物が担持された酸化チタンを含有する酸化チタン組成物を得た。
(2) Manufacturing process a) Mixing process (reaction process)
600 parts by mass of titanium oxide, 8 parts by mass of copper (ii) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Then, the mixture was stirred with a stirrer (“Robomics” manufactured by Tokushu Kagaku Kogyo Co., Ltd.), and a 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10.
b) Dehydration step Vacuum filtration was performed under reduced pressure using a qualitative filter paper (5C), solid content was separated from the mixed solution, and further washing was carried out with ion-exchanged water. Then, the washed solid was dried at 120 ° C. for 12 hours to remove water. After drying, a powdery titanium oxide composition was obtained by a mill (“Miller” manufactured by Iwatani Corporation).
c) Heat treatment step A titanium oxide composition containing titanium oxide carrying a divalent copper compound is heat-treated at 450 ° C. for 3 hours in the presence of oxygen using a precision thermostat (“DH650” manufactured by Yamato Kagaku Co., Ltd.). Obtained.
［光触媒の調整例２］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：１３ｍ２／ｇ
・ルチル化率：９５．６％
・１次粒子径：０．１５μｍ
[Photocatalyst adjustment example 2]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Manufacturing method: Gas phase method c) Physical characteristics / BET specific surface area: 13 m 2 / g
-Rutilation rate: 95.6%
-Primary particle size: 0.15 μm
調整例１において、酸化チタンの種類を前記酸化チタンに変更し、水の使用量を９００質量部から４，０００質量部に変更した以外は、調整例１と同様にして、酸化チタン組成物を得た。 In Adjustment Example 1, the titanium oxide composition was prepared in the same manner as in Adjustment Example 1 except that the type of titanium oxide was changed to the titanium oxide and the amount of water used was changed from 900 parts by mass to 4,000 parts by mass. Obtained.
［酸化チタン（ａ）への２価銅化合物の担持量の測定方法］
調整例で得られた酸化チタン組成物を、フッ酸溶液で全溶解し、抽出液をＩＣＰ発光分光分析装置により分析して、酸化チタン（ａ）に対する２価銅化合物の担持量（２価銅化合物の担持量（質量部）／酸化チタン（ａ）（質量部））を定量した。その結果、調整例１、調整例２のいずれも酸化チタン１００質量部に対して、銅イオンが０．５質量部であった。
[Method for measuring the amount of divalent copper compound supported on titanium oxide (a)]
The titanium oxide composition obtained in the adjusted example was completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectrophotometer to carry an amount of the divalent copper compound on titanium oxide (a) (divalent copper). The amount of the compound carried (parts by mass) / titanium oxide (a) (parts by mass)) was quantified. As a result, in both Adjustment Example 1 and Adjustment Example 2, copper ions were 0.5 parts by mass with respect to 100 parts by mass of titanium oxide.
［ウレタン樹脂組成物の調製］
＜ウレタン樹脂組成物の材料＞
・クリスボンＮＢ－１３０（ポリエーテル－ポリエステル系難黄変ウレタン樹脂溶液(ＤＩＣ社製）、１液型ウレタン樹脂、樹脂固形分：３０質量％、ＤＭＦ：７０質量％）
・ダイラックホワイトＬ－６７２５（着色剤（ＤＩＣ社製）、ルチル型の顔料級酸化チタン；５０％、ＤＭＦ；４０％、ウレタン樹脂固形分；１０％）
・クリスボンＴＡ－２６５（ポリエーテル系難黄変ウレタン樹脂溶液（ＤＩＣ社製）、２液型ウレタン樹脂、樹脂固形分：６５質量％、ＤＭＦ：３５質量％）
・バーノックＤＮ－９５０（ポリイソシアネート化合物(ＤＩＣ社製、樹脂固形分：７５質量％、酢酸エチル：２５質量％）
・クリスボンアクセルＴ－８１Ｅ：架橋促進剤（ＤＩＣ社製）
[Preparation of urethane resin composition]
<Material of urethane resin composition>
-Chrisbon NB-130 (polyester-polyester-based refractory urethane resin solution (manufactured by DIC), one-component urethane resin, resin solid content: 30% by mass, DMF: 70% by mass)
Dyrac White L-6725 (colorant (manufactured by DIC), rutile-type pigment grade titanium oxide; 50%, DMF; 40%, urethane resin solid content; 10%)
-Chrisbon TA-265 (polyether-based refractory urethane resin solution (manufactured by DIC), two-component urethane resin, resin solid content: 65% by mass, DMF: 35% by mass)
-Bernock DN-950 (polyisocyanate compound (manufactured by DIC Corporation, resin solid content: 75% by mass, ethyl acetate: 25% by mass))
-Chrisbon Accelerator T-81E: Crosslinking accelerator (manufactured by DIC Corporation)
＜ウレタン樹脂組成物の組成＞
表皮層用樹脂組成物Ａは次の材料をホモミキサーで混合して得た。
（１）クリスボンＮＢ－１３０ １００質量部
（２）ＤＭＦ ４０質量部
（３）ダイラックホワイトＬ－６７２５ １５質量部
（４）調整例１または調整例２ ０．５～１５質量部
<Composition of urethane resin composition>
The resin composition A for the epidermis layer was obtained by mixing the following materials with a homomixer.
(1) Chrisbon NB-130 100 parts by mass (2) DMF 40 parts by mass (3) Dyrac White L-6725 15 parts by mass (4) Adjustment Example 1 or Adjustment Example 2 0.5 to 15 parts by mass
表皮層用樹脂組成物Ｂは次の材料をホモミキサーで混合して得た。
（１）クリスボンＮＢ－１３０ １００質量部
（２）ＤＭＦ ４０質量部
（３）ダイラックホワイトＬ－６７２５ １５質量部
The resin composition B for the epidermis layer was obtained by mixing the following materials with a homomixer.
(1) Chris Bonn NB-130 100 parts by mass (2) DMF 40 parts by mass (3) Dyrac White L-6725 15 parts by mass
接着層用樹脂組成物は次の材料をホモミキサーで混合して得た。
（１）クリスボンＴＡ－２６５ １００質量部
（２）ＤＭＦ ２０質量部
（３）ＭＥＫ ２０質量部
（４）バーノックＤＮ－９５０ １２質量部
（５）クリスボンアクセルＴ－８１Ｅ ３質量部
The resin composition for the adhesive layer was obtained by mixing the following materials with a homomixer.
(1) Lisbon TA-265 100 parts by mass (2) DMF 20 parts by mass (3) MEK 20 parts by mass (4) Barnock DN-950 12 parts by mass (5) Lisbon accelerator T-81E 3 parts by mass
表面処理剤樹脂組成物Ａは次の材料をホモミキサーで混合して得た。
（１）クリスボンＮＢ－１３０ １００質量部
（２）ＤＭＦ １００質量部
（３）ＭＥＫ １００質量部
（４）調整例１または調整例２ ５質量部
The surface treatment agent resin composition A was obtained by mixing the following materials with a homomixer.
(1) Chrisbon NB-130 100 parts by mass (2) 100 parts by mass of DMF (3) 100 parts by mass of MEK (4) Adjustment example 1 or adjustment example 2 5 parts by mass
表面処理剤樹脂組成物Ｂは次の材料をホモミキサーで混合して得た。
（１）クリスボンＮＢ－１３０ １００質量部
（２）ＤＭＦ １００質量部
（３）ＭＥＫ １００質量部
The surface treatment agent resin composition B was obtained by mixing the following materials with a homomixer.
(1) Chris Bonn NB-130 100 parts by mass (2) 100 parts by mass of DMF (3) 100 parts by mass of MEK
［評価用サンプル作製方法］
次の乾式成膜法によって評価用人工皮革を作製した。
離型紙（旭ロール株式会社製の製品名「アサヒリリースＡＲ－１９１」）上に、表皮層用樹脂組成物ＡまたはＢを厚み１５０μｍ（乾燥時膜厚約３０μｍ）になるようにドクターナイフで塗布した後、１２０℃で２分間熱風乾燥させた。次に、その表皮層の乾燥塗膜上に、接着層用樹脂組成物を厚み１５０μｍ（乾燥時膜厚約５０μｍになるようにドクターナイフで塗布した後、７０℃で１分間熱風で予備乾燥させた。更に、予備乾燥させた接着層を不織布と貼り合わせた後、１２０℃で２分間熱風乾燥させた。その後、７０℃で１２時間エージングした後、離型紙を剥がすことにより、評価用人工皮革を作製した。
さらに表面処理を施す場合、表面処理剤樹脂組成物ＡまたはＢをグラビアコーターにて厚み２０μm（乾燥時膜厚７μｍ）になるように塗布した後、８０℃で２分熱風乾燥させた。
[Method for preparing samples for evaluation]
An artificial leather for evaluation was produced by the following dry film forming method.
Apply the resin composition A or B for the epidermis layer on the release paper (product name "Asahi Release AR-191" manufactured by Asahi Roll Co., Ltd.) with a doctor knife so that the thickness is 150 μm (thickness when dried is about 30 μm). Then, it was dried with hot air at 120 ° C. for 2 minutes. Next, the resin composition for the adhesive layer was applied onto the dry coating film of the skin layer with a doctor knife so as to have a thickness of 150 μm (thickness at the time of drying was about 50 μm), and then pre-dried at 70 ° C. for 1 minute with hot air. Further, the pre-dried adhesive layer was bonded to the non-woven fabric and then dried with hot air at 120 ° C. for 2 minutes. Then, after aging at 70 ° C. for 12 hours, the release paper was peeled off to make an artificial leather for evaluation. Was produced.
When further surface-treating, the surface-treating agent resin composition A or B was applied with a gravure coater to a thickness of 20 μm (thickness at the time of drying was 7 μm), and then dried with hot air at 80 ° C. for 2 minutes.
［抗ウイルス性の評価方法］
上記で得られた評価用人工皮革について、抗ファージウイルス試験（フィルム密着法、ＪＩＳ Ｒ１７５６：２０２０を参照）を実施した。
[Evaluation method of antiviral property]
The evaluation artificial leather obtained above was subjected to an anti-phage virus test (see Film Adhesion Method, JIS R1756: 2020).
１）光照射条件は、白色蛍光灯の光をＮ１１３フィルターによって紫外線をカットし、照度１０００ルクスとした。
２）５ｃｍ×５ｃｍの評価用人工皮革に濃度既知の１００μＬのＱβファージ溶液を垂らした後、４ｃｍ×４ｃｍの密着フィルムをかぶせ、評価用のサンプルとした。
３）２時間光照射したサンプルを、ＳＣＤＬＰ液で回収し、適度に希釈したものを大腸菌と感染させ、寒天培地に塗布し、培養後のコロニー数をカウントすることで評価した。抗ウイルス性はＱβファージの不活化度で評価し、不活化度－２～－５を抗ウイルス性有と評価した。
1) As for the light irradiation condition, the light of the white fluorescent lamp was cut off from ultraviolet rays by the N113 filter, and the illuminance was set to 1000 lux.
2) A 100 μL Qβ phage solution having a known concentration was dropped on a 5 cm × 5 cm artificial leather for evaluation, and then covered with a 4 cm × 4 cm adhesive film to prepare a sample for evaluation.
3) Samples irradiated with light for 2 hours were collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, applied to an agar medium, and evaluated by counting the number of colonies after culturing. The antiviral property was evaluated by the degree of inactivation of Qβ phage, and the inactivation degree -2 to -5 was evaluated as having antiviral property.
不活化度は明所におけるファージ感染価の減少度を示すｌｏｇ（Ｎ／Ｎ０）の値である。Ｎは反応後のサンプルの感染価（ｐｆｕ／ｍｍ２）、Ｎ０は接種ファージの感染価（ｐｆｕ／ｍｍ２）である。不活化度－１が９０％、不活化度－２が９９％、不活化度－３が９９．９％、不活化度－４が９９．９９％、不活化度－５が９９．９９９％のウイルスが不活化していることを示し、抗ウイルス性が高いことを示す。 The degree of inactivation is a log (N / N 0 ) value indicating the degree of decrease in the phage infectivity titer in a bright place. N is the infectious titer of the sample after the reaction (pfu / mm 2 ), and N 0 is the infectious titer of the inoculated phage (pfu / mm 2 ). Inactivation degree -1 is 90%, inactivation degree -2 is 99%, inactivation degree -3 is 99.9%, inactivation degree -4 is 99.99%, inactivation degree -5 is 99.999%. Indicates that the virus is inactivated and has high antiviral properties.
＜実施例１＞
・表皮層用樹脂組成物Ａ；調整例１を５質量部添加
・表面処理剤なし
（評価結果）不活性度；－３ →抗ウイルス性あり
<Example 1>
・ Resin composition A for epidermis layer; 5 parts by mass of Adjustment Example 1 added ・ No surface treatment agent (evaluation result) Inactivity; -3 → Antiviral
＜実施例２＞
・表皮層用樹脂組成物Ａ；調整例１を１５質量部添加
・表面処理剤なし
（評価結果）不活性度；－５ →抗ウイルス性あり
<Example 2>
-Resin composition A for epidermis layer; 15 parts by mass of Adjustment Example 1 added-No surface treatment agent (evaluation result) Inactivity; -5 → Antiviral
＜実施例３＞
・表皮層用樹脂組成物Ａ；調整例２を５質量部添加
・表面処理剤なし
（評価結果）不活性度；－３ →抗ウイルス性あり
<Example 3>
・ Resin composition A for epidermis layer; 5 parts by mass of Adjustment Example 2 added ・ No surface treatment agent (evaluation result) Inactivity; -3 → Antiviral
＜実施例４＞
・表皮層用樹脂組成物Ａ；調整例１を０．５質量部添加
・表面処理剤なし
（評価結果）不活性度；－２ →抗ウイルス性あり
<Example 4>
-Resin composition A for epidermis layer; 0.5 parts by mass of Adjustment Example 1 added-No surface treatment agent (evaluation result) Inactivity; -2 → Antiviral
＜実施例５＞
・表皮層用樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
・表面処理剤あり。表面処理樹脂組成物Ａに調整例１を５質量部添加
（評価結果）不活性度；－３ →抗ウイルス性あり
<Example 5>
-Resin composition B for epidermis layer; neither adjustment example 1 nor adjustment example 2 is added and has a surface treatment agent. Addition of 5 parts by mass of Preparation Example 1 to the surface-treated resin composition A (evaluation result) Inactivity; -3 → Antiviral
＜実施例６＞
・表皮層用樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
・表面処理剤あり。表面処理樹脂組成物Ａに調整例２を５質量部添加
（評価結果）不活性度；－３ →抗ウイルス性あり
<Example 6>
-Resin composition B for epidermis layer; neither adjustment example 1 nor adjustment example 2 is added and has a surface treatment agent. Addition of 5 parts by mass of Adjustment Example 2 to the surface-treated resin composition A (evaluation result) Inactivity; -3 → Antiviral
＜実施例７＞
・表皮層用樹脂組成物Ａ；調整例１を５質量部添加
・表面処理剤あり。表面処理剤組成物Ａに調整例１を５質量部添加
（評価結果）不活性度；－４ →抗ウイルス性あり
<Example 7>
-Resin composition A for epidermis layer; 5 parts by mass of Adjustment Example 1 is added.-There is a surface treatment agent. Addition of 5 parts by mass of Preparation Example 1 to the surface treatment agent composition A (evaluation result) Inactivity; -4 → Antiviral
＜比較例１＞
・表皮層用樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
・表面処理剤なし
（評価結果）不活性度；－０．２ →抗ウイルス性なし
<Comparative Example 1>
-Resin composition B for epidermis layer; neither Adjustment Example 1 nor Adjustment Example 2 added-No surface treatment agent (evaluation result) Inactivity; -0.2 → No antiviral property
＜比較例２＞
・表皮層用樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
・表面処理剤あり。表面処理樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
（評価結果）不活性度；－０．２ →抗ウイルス性なし
<Comparative Example 2>
-Resin composition B for epidermis layer; neither adjustment example 1 nor adjustment example 2 is added and has a surface treatment agent. Surface-treated resin composition B; Not added in any of Adjustment Example 1 and Adjustment Example 2 (evaluation result) Inactivity; -0.2 → No antiviral property
＜比較例３＞
・表皮層用樹脂組成物Ａ；調整例１を５質量部添加
・表面処理剤あり。表面処理樹脂組成物Ｂ；調整例１、調整例２のいずれも未添加
（評価結果）不活性度；－０．２ →抗ウイルス性なし
<Comparative Example 3>
-Resin composition A for epidermis layer; 5 parts by mass of Adjustment Example 1 is added.-There is a surface treatment agent. Surface-treated resin composition B; Not added in any of Adjustment Example 1 and Adjustment Example 2 (evaluation result) Inactivity; -0.2 → No antiviral property
［ウレタン樹脂造形物の製造］
以下に、本発明のウレタン樹脂組成物を用いた造形物の製造に係る実施例を記載する。
[Manufacturing of urethane resin model]
Hereinafter, examples relating to the production of a model using the urethane resin composition of the present invention will be described.
［ウレタン樹脂組成物の調製］
＜ウレタン樹脂組成物の材料＞
パンテックス Ｔ－９２９０（ポリカーボネート系熱可塑性ウレタン（ディーアイシーコベストロポリマ―社製））、イルガノックス１０１０(フェノール系酸化防止剤(BASF社製))
[Preparation of urethane resin composition]
<Material of urethane resin composition>
Pantex T-9290 (Polycarbonate-based thermoplastic urethane (manufactured by DIC CobestroPolymer)), Irganox 1010 (Phenolic-based antioxidant (manufactured by BASF))
＜ウレタン樹脂組成物の組成＞
造形物用組成物Aは、溶融混錬押出により下記の原料を混錬し、フィラメントを得た。
（１）パンテックス Ｔ－９２９０ １００質量部
（２）調整例１ １１質量部
（３）イルガノックス１０１０ ０．３～０．４質量部
<Composition of urethane resin composition>
For the composition A for modeling, the following raw materials were kneaded by melt-kneading extrusion to obtain filaments.
(1) Pantex T-9290 100 parts by mass (2) Adjustment example 1 11 parts by mass (3) Irganox 1010 0.3 to 0.4 parts by mass
造形物用組成物Ｂは溶融混錬押出により下記の原料を混錬し、フィラメントを得た。
（１）パンテックス Ｔ－９２９０ １００質量部
（２）調整例１ ２５質量部
（３）イルガノックス１０１０ ０．３～０．４質量部
The composition B for a model was kneaded with the following raw materials by melt-kneading extrusion to obtain a filament.
(1) Pantex T-9290 100 parts by mass (2) Adjustment example 1 25 parts by mass (3) Irganox 1010 0.3 to 0.4 parts by mass
［評価用サンプル作製方法］
調整例１無添加品（パンテックス Ｔ－９２９０ １００重量部）、及び前記の造形物用組成物Ａ、Ｂを更に溶融混錬押出によりフィラメント形態に加工し、フィラメント径２．８５ｍｍφのフィラメントを得た。
[Method for preparing samples for evaluation]
Adjustment Example 1 Additive-free product (Pantex T-9290 100 parts by weight) and the above-mentioned compositions A and B for shaped objects are further processed into a filament form by melt-kneading extrusion to obtain a filament having a filament diameter of 2.85 mmφ. rice field.
前記のフィラメントにより、三次元造形装置（Ｕｌｔｉｍａｋｅｒ社製）により熱溶融積層造形を行い、サイズ６０ｍｍ×６０ｍｍ×２ｍｍの造形物を作製。前記造形物をサイズ５０ｍｍ×５０ｍｍ×２ｍｍに調整し評価用サンプルを得た。 Using the above filament, hot melt lamination modeling is performed with a three-dimensional modeling device (manufactured by Ultimaker) to produce a model with a size of 60 mm × 60 mm × 2 mm. The model was adjusted to a size of 50 mm × 50 mm × 2 mm to obtain an evaluation sample.
［抗ウイルス性の評価方法］
前記で得た評価用サンプルについて、抗ウイルス試験（ＩＳＯ２１７０２（ＪＩＳ Ｚ２８０１）を参照）を実施した。
[Evaluation method of antiviral property]
An antiviral test (see ISO21702 (JIS Z2801)) was performed on the evaluation sample obtained above.
１）評価用サンプルの調整例１無添加品、及び造形物用組成物Ａ、Ｂに０．４ｍｌのウイルス液を滴下し、サイズ４０ｍｍ×４０ｍｍのフィルムで被覆。
２）２５℃×２４時間静置。
３）静置後、試験片上のウイルスを洗い出して回収した後、ウイルス感染価を測定。
1) Example of preparation of evaluation sample 1 0.4 ml of virus solution was dropped onto additive-free products and compositions A and B for shaped objects, and coated with a film having a size of 40 mm × 40 mm.
2) Stand at 25 ° C for 24 hours.
3) After standing still, the virus on the test piece was washed out and recovered, and then the virus infectivity was measured.
前記ウイルス試験のウイルスは、Ａ型インフルエンザウイルス（Ｈ３Ｎ２）で行い、次式によりウイルスが減少した百分率（ウイルス減少率％）を算出し、ウイルス減少率９５％以上を抗ウイルス性ありと評価した。
式）Ｒ＝（Ｕｔ－Ａｔ）／Ｕｔ×１００
Ｒ：ウイルス減少率％
Ｕｔ：調整例１無添加品の24時間静置後のウイルス感染価（ＰＦＵ／ｃｍ２）の平均値
Ａｔ：造形物用組成物Ａ、Ｂの24時間静置後のウイルス感染価（ＰＦＵ／ｃｍ２）の平均値
The virus in the virus test was influenza A virus (H3N2), and the percentage of virus reduction (virus reduction rate%) was calculated by the following formula, and a virus reduction rate of 95% or more was evaluated as having antiviral properties.
Equation) R = (Ut-At) / Ut × 100
R: Virus reduction rate%
Ut: Adjustment Example 1 Average value of virus infectivity (PFU / cm 2 ) of additive-free product after 24 hours of standing At: Virus infectivity of compositions A and B for modeling after 24 hours of standing (PFU / cm 2) cm 2 ) average value
＜比較例４＞
調整例１無添加品
（評価結果）
・Ａ型インフルエンザウイルス（Ｈ３Ｎ２）；ウイルス減少率０％→抗ウイルス性なし
<Comparative Example 4>
Adjustment example 1 Additive-free product (evaluation result)
・ Influenza A virus (H3N2); virus reduction rate 0% → no antiviral property
＜実施例８＞
造形物用組成物Ａ
（評価結果）
・Ａ型インフルエンザウイルス（Ｈ３Ｎ２）； ウイルス減少率９７％→抗ウイルス性あり
<Example 8>
Composition A for modeling
(Evaluation results)
・ Influenza A virus (H3N2); virus reduction rate 97% → anti-virus
＜実施例９＞
造形物用組成物Ｂ
（評価結果）
・Ａ型インフルエンザウイルス（Ｈ３Ｎ２）； ウイルス減少率９９％→抗ウイルス性あり
<Example 9>
Composition B for modeling
(Evaluation results)
・ Influenza A virus (H3N2); virus reduction rate 99% → anti-virus
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