JP2015072159A - Coating composition for radiation shielding sheet, method for manufacturing radiation shielding sheet and radiation shielding sheet - Google Patents
Coating composition for radiation shielding sheet, method for manufacturing radiation shielding sheet and radiation shielding sheet Download PDFInfo
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- JP2015072159A JP2015072159A JP2013207174A JP2013207174A JP2015072159A JP 2015072159 A JP2015072159 A JP 2015072159A JP 2013207174 A JP2013207174 A JP 2013207174A JP 2013207174 A JP2013207174 A JP 2013207174A JP 2015072159 A JP2015072159 A JP 2015072159A
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- Prior art keywords
- radiation shielding
- weight
- coating composition
- shielding sheet
- group
- Prior art date
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- 230000005855 radiation Effects 0.000 title claims abstract description 71
- 239000008199 coating composition Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 title description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 17
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 125000000962 organic group Chemical group 0.000 claims abstract description 9
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 230000001681 protective effect Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- -1 γ- chloropropyl group Chemical group 0.000 description 17
- 239000002253 acid Substances 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000005251 gamma ray Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application 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
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
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- 229910052582 BN Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、放射線医療従事者や原子力発電所作業、原子力災害被害者等が、Ｘ線や放射線の被曝を防ぐ放射線遮蔽防護服や放射線治療用の放射線遮蔽防護服に用いられる放射線遮蔽シート用のコーティング組成物、これを用いた放射線遮蔽シートに関する。 The present invention provides a radiation shielding sheet for use in radiation shielding protective clothing and radiation shielding protective clothing for radiation medical workers, nuclear power plant operations, nuclear disaster victims, etc. to prevent exposure to X-rays and radiation. The present invention relates to a coating composition and a radiation shielding sheet using the same.
放射線遮蔽防護服に用いられる放射線遮蔽材に関しては、例えば、特開２００４-７７１７０号公報（特許文献１）に開示のものが知られている。特開２００４-７７１７０号公報の開示は、発明名称「放射線遮蔽材及びこれを用いた放射線遮蔽用防護衣」に係り、「環境への影響が少なく、装着性、使用性が良好で、しかも折り曲げ等に対する強度が良好な放射線遮蔽材、放射線遮蔽用防護衣、及びその製造方法を提供することにある。更に、放射線遮蔽材に生じたひび割れ、亀裂等の損傷を従来のＸ線検査によらずとも、簡易な方法で確認できる放射線遮蔽用防護衣を提供する。」ことを目的とする発明解決課題において(同公報明細書段落番号０００６参照）、「（１）タングステン粉末を主成分とする非鉛系無機粉末と、（２）熱可塑性エラストマーを含有する、比重５以上の高比重シート１の表裏両面にカバー材２を配置した」構成とすることにより（同公報特許請求の範囲請求項１の記載等参照）、「装着性、使用性が良好で、しかも折り曲げ等に対する強度が良好な放射線遮蔽用防護衣を提供することができる。また、タングステン粉末を主成分とする非鉛無機粉末と熱可塑性エラストマーを含有する高比重シートを放射線遮蔽材として使用しているため、鉛のような環境汚染の問題はない。更に、保管の際に生じやすい高比重シート破損の有無は、カバー材を透明性のある材料にするか、又はカバー材の一部又は全体にファスナー等を付けて開閉式にすることによって、容易に確認することができる。」等の効果を奏するものである（同公報明細書段落番号００３５参照）。
しかしながら、特許文献１の放射線遮蔽材は、単にタングステン粉末と熱可塑性エラストマーを主成分とするが、比重が５以上と重く、作業性や取り扱い性に問題点がある。
As a radiation shielding material used for radiation shielding protective clothing, for example, a material disclosed in Japanese Patent Application Laid-Open No. 2004-77170 (Patent Document 1) is known. The disclosure of Japanese Patent Application Laid-Open No. 2004-77170 relates to the invention name “radiation shielding material and radiation shielding protective clothing using the same”, “less impact on the environment, good wearability and usability, and folding. It is another object of the present invention to provide a radiation shielding material, a radiation shielding protective garment, and a method for manufacturing the same, and to protect the radiation shielding material from cracks, cracks, and other damage caused by conventional X-ray inspection. In both cases, the invention provides a radiation shielding protective garment that can be confirmed by a simple method (see paragraph number 0006 of the same gazette specification). The cover material 2 is disposed on both the front and back surfaces of a high specific gravity sheet 1 containing a lead-based inorganic powder and (2) a thermoplastic elastomer and having a specific gravity of 5 or more. 1), “a protective clothing for radiation shielding with good wearability and usability and good strength against bending, etc. can also be provided. Also, a lead-free inorganic powder mainly composed of tungsten powder And high-density sheet containing thermoplastic elastomer is used as a radiation shielding material, so there is no problem of environmental pollution such as lead. Can be easily confirmed by using a transparent material, or by attaching a fastener or the like to a part or the whole of the cover material to make it openable. ” (See publication specification, paragraph number 0035).
However, although the radiation shielding material of Patent Document 1 is mainly composed of tungsten powder and a thermoplastic elastomer, the specific gravity is as heavy as 5 or more, and there are problems in workability and handleability.
また、本発明者も、既に放射線遮蔽材を提案している（ＷＯ２０１３／０１８５１２、特許文献２）。しかしながら、この遮蔽材は、放射線遮蔽としては優れたものではあったが、固くてゴワゴワ感があり、とても人体の身につけて動き回れるようなものではなかった。 In addition, the present inventor has already proposed a radiation shielding material (WO2013 / 018512, Patent Document 2). However, although this shielding material was excellent as a radiation shielding, it was hard and stiff, and it was not something that could be worn around the human body.
本発明は、人体に容易に装着可能で、装着後も容易に動き回ることができる放射線遮蔽にも効果を有する放射線遮蔽防護服用の放射線遮蔽シートを提供することが可能な放射線遮蔽シート用のコーティング組成物、これを用いた放射線遮蔽シートを提供することを目的とする。 The present invention relates to a coating composition for a radiation shielding sheet capable of providing a radiation shielding sheet for a radiation shielding protective clothing that can be easily worn on a human body and can be easily moved after wearing, and also has an effect on radiation shielding. An object is to provide a radiation shielding sheet using the same.
本発明は、（ａ）オルガノアルコキシシラン、その加水分解物、およびその縮合物の群から選ばれた少なくとも１種からなるオルガノシロキサン類をオルガノアルコキシシラン換算で１０〜３０重量％、（ｂ）アクリル樹脂１０〜３０重量％、（ｃ）親水性有機溶剤１０〜６０重量％、および（ｄ）水１０〜７０重量％（ただし、（ａ）＋（ｂ）＋（ｃ）＋（ｄ）＝１００重量％）の合計量１００重量部に対し、（ｅ）タングステン粉末を１００〜２００重量部含有し、固形分濃度が１０〜４０重量％である、放射線遮蔽シート用コーティング組成物に関する。
ここで、（ａ）成分を構成するオルガノアルコキシシランとしては、Ｒ1 Ｓｉ（ＯＲ2 ）3（式中、Ｒ1 は炭素数１〜８の有機基、Ｒ2 は同一又は異なり、炭素数１〜５のアルキル基および／または炭素数１〜４のアシル基を表す）で表されるオルガノトリアルコキシシランが好ましい。
また、（ａ）成分を構成するオルガノアルコキシシランには、さらにＲ1 ２Ｓｉ（ＯＲ2 ）２（式中、Ｒ1 は同一または異なり、炭素数１〜８の有機基、Ｒ2 は同一又は異なり、炭素数１〜５のアルキル基および／または炭素数１〜４のアシル基を表す）で表されるジオルガノジアルコキシシランを含んでいてもよい。
さらに、上記（ｃ）タングステン粉末の粒度は、３〜１０μｍである。
次に、本発明は、布帛からなる基材に、上記コーティング組成物を塗布し、８０〜１５０℃で、１０〜６０分、乾燥させることを特徴とする、放射線遮蔽シートの製造方法、この製造方法によって得られる放射線遮蔽シートに関する。
次に、本発明は、布帛からなる基材に、上記コーティング組成物を塗布し、８０〜１５０℃で、１０〜６０分、乾燥させたのち、当該基材を除去することを特徴とする、放射線遮蔽シートの製造方法、この製造方法によって得られる放射線遮蔽シートに関する。
The present invention relates to (a) an organoalkoxysilane, hydrolyzate thereof, and at least one organosiloxane selected from the group of condensates thereof in an amount of 10 to 30% by weight in terms of organoalkoxysilane, and (b) acrylic. 10-30 wt% resin, (c) 10-60 wt% hydrophilic organic solvent, and (d) 10-70 wt% water (where (a) + (b) + (c) + (d) = 100 It relates to a coating composition for a radiation shielding sheet containing 100 to 200 parts by weight of (e) tungsten powder and having a solid content concentration of 10 to 40% by weight with respect to 100 parts by weight of the total amount of (% by weight).
Here, as the organoalkoxysilane constituting the component (a), R 1 Si (OR 2 ) 3 (wherein R 1 is an organic group having 1 to 8 carbon atoms, R 2 is the same or different and has 1 carbon atom) Represents an alkyl group having ˜5 and / or an acyl group having 1 to 4 carbon atoms).
In addition, the organoalkoxysilane constituting the component (a) further includes R 1 2 Si (OR 2 ) 2 (wherein R 1 is the same or different, the organic group having 1 to 8 carbon atoms, and R 2 is the same or And a diorganodialkoxysilane represented by a C 1-5 alkyl group and / or a C 1-4 acyl group).
Furthermore, the particle size of the (c) tungsten powder is 3 to 10 μm.
Next, this invention applies the said coating composition to the base material which consists of fabrics, and it is made to dry at 80-150 degreeC for 10 to 60 minutes, This manufacturing method of a radiation shielding sheet characterized by the above-mentioned The present invention relates to a radiation shielding sheet obtained by the method.
Next, the present invention is characterized in that the above-mentioned coating composition is applied to a substrate made of a fabric, dried at 80 to 150 ° C. for 10 to 60 minutes, and then the substrate is removed. The present invention relates to a method for producing a radiation shielding sheet and a radiation shielding sheet obtained by this production method.
本発明によれば、人体に容易に装着可能で、装着後も容易に動き回ることができる放射線遮蔽にも効果を有する放射線遮蔽防護服用の放射線遮蔽シートを提供することが可能な放射線遮蔽シート用のコーティング組成物、これを用いた放射線遮蔽シートを提供することを目的とする。 According to the present invention, a radiation shielding sheet for a radiation shielding sheet capable of providing a radiation shielding sheet for a radiation shielding protective clothing that can be easily attached to a human body and that can easily move around after being attached and that is also effective for radiation shielding. An object of the present invention is to provide a coating composition and a radiation shielding sheet using the same.
＜（ａ）オルガノアルコキシシラン類＞
（ａ）オルガノアルコキシシラン類としては、式（１）：Ｒ1 Ｓｉ（ＯＲ2 ）3 （式中、Ｒ1 は炭素数１〜８の有機基、Ｒ2は同一または異なり、炭素数１〜５のアルキル基および／または炭素数１〜４のアシル基を表す）で表されるオルガノアルコキシシラン（以下「オルガノアルコキシシラン（１）」ともいう）、その加水分解物、あるいはその縮合物が挙げられる。（ａ）成分は、エマルジョン（コロイド状も含む）でも、溶剤系でもよい。
なお、（ａ）オルガノアルコキシシラン類には、式（２）；Ｒ1 ２ Ｓｉ（ＯＲ2）２（式中、Ｒ1 は同一または異なり、炭素数１〜８の有機基、Ｒ2は同一または異なり、炭素数１〜５のアルキル基および／または炭素数１〜４のアシル基を表す）で表されるオルガノアルコキシシラン（以下「オルガノアルコキシシラン（２）」ともいう）、その加水分解物、あるいはその縮合物を（ａ）成分中、５０重量％以下程度併用することができる。
<(A) Organoalkoxysilanes>
(A) As organoalkoxysilanes, formula (1): R 1 Si (OR 2 ) 3 (wherein R 1 is an organic group having 1 to 8 carbon atoms, R 2 is the same or different, and 1 to 5 represents an alkyl group of 5 and / or an acyl group having 1 to 4 carbon atoms), a hydrolyzate thereof, or a condensate of the organoalkoxysilane (hereinafter also referred to as “organoalkoxysilane (1)”). It is done. The component (a) may be an emulsion (including colloidal form) or a solvent system.
In addition, (a) organoalkoxysilane includes formula (2); R 1 2 Si (OR 2 ) 2 (wherein, R 1 is the same or different, an organic group having 1 to 8 carbon atoms, R 2 is the same or different, an alkyl group having 1 to 5 carbon atoms and / or a carbon number having 1 to 4 carbon atoms) An organoalkoxysilane (hereinafter also referred to as “organoalkoxysilane (2)”) represented by an acyl group), a hydrolyzate thereof, or a condensate thereof is used in combination with about 50% by weight or less in the component (a). Can do.
（ａ）成分を構成するオルガノアルコキシランは、水の存在により酸またはアルカリの存在下もしくは非存在下で加水分解および重縮合して高分子量化するものであり、その塗膜は加熱下または常温下で硬化する。また、本発明のコーティング組成物においては、有機質の（ｂ）アクリル樹脂と（ｃ）タングステン粉末との親和性を向上させるとともに、タングステン粉末を組成物中に均質に分散する分散剤として作用する。 The organoalkoxylane constituting the component (a) is hydrolyzed and polycondensed in the presence or absence of acid or alkali in the presence of water to increase the molecular weight, and the coating film is heated or at room temperature. Cure under. Moreover, in the coating composition of this invention, while improving the affinity of organic (b) acrylic resin and (c) tungsten powder, it acts as a dispersing agent which disperse | distributes tungsten powder uniformly in a composition.
ここで、オルガノアルコキシシランの加水分解触媒となる酸としては、塩酸、硝酸、硫酸、リン酸、ギ酸、酢酸なとどが挙げられる。また、加水分解触媒となる塩基としては、アンモニア、水酸化テトラメチルアンモニウム、水酸化２−ヒドロキシエチルトリメチルアンモニウム、エタノールアミン、ジエタノールアミン、トリエタノールアミンなどが挙げられる。なお、これらの通常の触媒を用いる場合には、加水分解の際に、反応水を共存させる。 Here, examples of the acid that serves as a hydrolysis catalyst for the organoalkoxysilane include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, and acetic acid. Examples of the base that serves as a hydrolysis catalyst include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine, diethanolamine, and triethanolamine. In addition, when using these normal catalysts, reaction water is made to coexist in the case of a hydrolysis.
かかるオルガノアルコキシシラン（１）は、前記式中のＲ1 が炭素数１〜８の有機基、例えばメチル基、エチル基、ｎ−プロピル基などのアルキル基、そのほかγ−クロロプロピル基、ビニル基、３，３，３−トリフロロプロピル基、γ−グリシドキシプロピル基、γ−メタクリルオキシプロピル基、γ−メルカプトプロピル基、フェニル基、３，４−エポキシシクロヘキシルエチル基、γ−アミノプロピル基などであり、また式中のＲ2 は同一または異なり、炭素数１〜５のアルキル基および／または炭素数１〜４のアシル基、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、アセチル基などである有機シラン化合物である。 Such organoalkoxysilane (1), R 1 is an organic group having 1 to 8 carbon atoms in the above formula, for example a methyl group, an ethyl group, an alkyl group such as n- propyl group, other γ- chloropropyl group, a vinyl group 3,3,4-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group, γ-aminopropyl group R 2 in the formula is the same or different and is an alkyl group having 1 to 5 carbon atoms and / or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group. Group, an n-butyl group, a sec-butyl group, a t-butyl group, an acetyl group, and the like.
これらのオルガノアルコキシシラン（１）の具体例として、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ｉ−プロピルトリメトキシシラン、ｉ−プロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３，３，３−トリフロロプロピルトリメトキシシラン、３，３，３−トリフロロプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、３，４−エポキシシクロヘキシルエチルメトキシシラン、３，４−エポキシシクロヘキシルエチルエトキシシラン、γ−アミノプロピルメトキシシラン、γ−アミノプロピルエトキシシランなどを例示できる。 Specific examples of these organoalkoxysilanes (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyl. Trimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethylmethoxysilane, 3,4-epoxycyclohexylethylethoxy Examples include silane, γ-aminopropylmethoxysilane, γ-aminopropylethoxysilane, and the like.
これらのオルガノアルコキシシラン（１）は、１種の単独で使用してもよく、また２種以上を併用してもよい。好ましくは、メチルトリメトキシシランおよび／またはメチルトリエトキシシランを使用する。また、（ａ）成分としては、かかるオルガノアルコキシシランを、あらかじめ酸またはアルカリの存在下もしくは非存在下で加水分解した加水分解物、該加水分解物をさらに熟成して重縮合した縮合物を使用することもできる。縮合の度合いとしては、２〜１０分子程度の縮合体が挙げられる。 These organoalkoxysilanes (1) may be used alone or in combination of two or more. Preferably, methyltrimethoxysilane and / or methyltriethoxysilane are used. Further, as the component (a), a hydrolyzate obtained by hydrolyzing the organoalkoxysilane in the presence or absence of an acid or alkali in advance, or a condensate obtained by further aging the hydrolyzate and polycondensing the hydrolyzate is used. You can also Examples of the degree of condensation include condensates of about 2 to 10 molecules.
なお、（ａ）成分を構成するオルガノアルコキシシラン（２）の具体例としては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、メチルビニルジメトキシシラン、メチルビニルジエトキシシランなどや、これらの化合物の２〜１０分子程度の縮合体を例示することができる。
オルガノアルコキシシラン（２）の使用量は、（ａ）成分中に５０重量％以下程度であり、５０重量％を超えると、オルガノアルコキシシラン（１）とうまくシロキサン結合が生成せず好ましくない。オルガノアルコキシシラン(２)の使用量は、(ａ)成分中に、５０重量％以下、好ましくは５〜４０重量％、さらに好ましくは１０〜３０重量％程度ある。(ａ)成分中に、オルガノアルコキシシラン(２)を併用すると、得られるシートに柔軟性を付与することができる。
Specific examples of the organoalkoxysilane (2) constituting the component (a) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and methylvinyl. Examples include dimethoxysilane, methylvinyldiethoxysilane, and the like, and condensates of about 2 to 10 molecules of these compounds.
The amount of the organoalkoxysilane (2) used is about 50% by weight or less in the component (a). If it exceeds 50% by weight, a siloxane bond cannot be formed well with the organoalkoxysilane (1), which is not preferable. The amount of the organoalkoxysilane (2) used is 50% by weight or less, preferably 5 to 40% by weight, and more preferably about 10 to 30% by weight in the component (a). When organoalkoxysilane (2) is used in combination with component (a), flexibility can be imparted to the resulting sheet.
本発明の（ａ）成分は、オルガノアルコキシシランを水の存在下で、加水分解触媒として、酸や塩基などを用いて、加水分解、縮合させるから、得られる（ａ）成分は、オルガノアルコキシシラン、その加水分解物、その縮合物の混合物となり、反応水と生成するアルコール類の混合系であって、その形態は、溶剤系、エマルジョン、もしくはコロイド状である。 The component (a) of the present invention hydrolyzes and condenses the organoalkoxysilane in the presence of water using an acid or a base as a hydrolysis catalyst. , A hydrolyzate thereof, and a mixture of the condensate thereof, which is a mixed system of reaction water and generated alcohols, and its form is a solvent system, an emulsion, or a colloidal form.
なお、（ａ）成分の加水分解、縮合には、有機金属化合物を用いることもできる。この例示としては、例えばチタン、ジルコニウム、アルミニウムあるいはスズの錯体であり、テトラプロポキシチタン、テトラブトキシチタネート、テトラプロポキシジルコネート、テトラブトキシジルコネート、トリプロポキシアルミネート、アルミニウムアセチルアセトナート、ジブチルスズジアセテート、ジブチルスズジラウレートなどが挙げられる。 In addition, an organometallic compound can also be used for hydrolysis and condensation of the component (a). Examples thereof include, for example, complexes of titanium, zirconium, aluminum or tin, such as tetrapropoxy titanium, tetrabutoxy titanate, tetrapropoxy zirconate, tetrabutoxy zirconate, tripropoxy aluminate, aluminum acetylacetonate, dibutyltin diacetate, Examples include dibutyltin dilaurate.
（ａ）〜（ｄ）成分中における（ａ）成分の配合割合は、オルガノアルコキシシラン換算で１０〜３０重量％、好ましくは１０〜２０重量％である。（ａ）成分の配合割合が、１０重量％未満ではバインダーとしての効能がなくなり、一方３０重量％を超えると相対的にタングステン粉末の量が減って、放射線遮蔽能が低下する。 The blending ratio of the component (a) in the components (a) to (d) is 10 to 30% by weight, preferably 10 to 20% by weight in terms of organoalkoxysilane. When the blending ratio of the component (a) is less than 10% by weight, the effect as a binder is lost. On the other hand, when it exceeds 30% by weight, the amount of tungsten powder is relatively reduced, and the radiation shielding ability is lowered.
＜（ｂ）アクリル樹脂＞
（ｂ）アクリル樹脂としては、アクリル系単量体、およびアクリル系単量体と共重合可能な他の単量体とをラジカル共重合により得られるものが使用できる。
<(B) Acrylic resin>
(B) As an acrylic resin, what can be obtained by radical copolymerization of an acrylic monomer and the other monomer copolymerizable with an acrylic monomer can be used.
このうち、アクリル系単量体は、特に限定されないが、例えば、メチル（メタ）アクリレート（メチルアクリレートまたはメチルメタアクリレートのいずれかであることを示す。以下において同じ。）、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレートなどのアルキル基含有（メタ）アクリル系単量体；２-ヒドロキシエチル（メタ）アクリレートなどの水酸基含有（メタ）アクリル系単量体；（メタ）アクリル酸などのエチレン性不飽和カルボン酸；ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレートなどのアミノ基含有（メタ）アクリル系単量体；（メタ）アクリルアミド、エチル（メタ）アクリルアミドなどのアミド含有（メタ）アクリル系単量体；アクリロニトリルなどのニトリル基含有（メタ）アクリル系単量体；グリシジル（メタ）アクリレートなどのエポキシ基含有（メタ）アクリル系単量体等を例示できる。 Among these, the acrylic monomer is not particularly limited. For example, methyl (meth) acrylate (indicating that it is either methyl acrylate or methyl methacrylate; the same applies hereinafter), ethyl (meth) acrylate, Alkyl group-containing (meth) acrylic monomers such as n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) Hydroxyl group-containing (meth) acrylic monomers such as acrylate; ethylenically unsaturated carboxylic acid such as (meth) acrylic acid; amino group containing such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate (meta ) Acrylic monomer; (meth) aqua Amide-containing (meth) acrylic monomers such as rilamide and ethyl (meth) acrylamide; Nitrile group-containing (meth) acrylic monomers such as acrylonitrile; Epoxy group-containing (meth) acrylic monomers such as glycidyl (meth) acrylate A monomer etc. can be illustrated.
アクリル系単量体と共重合可能な他の単量体としては、スチレン、メチルスチレン、クロロスチレン、ビニルトルエンなどの芳香族炭化水素系ビニル単量体；マレイン酸、イタコン酸、クロトン酸、フマル酸、シトラコン酸などの瘁C竅|エチレン性不飽和カルボン酸；スチレンスルホン酸、ビニルスルホン酸などのスルホン酸含有ビニル単量体；無水マレイン酸、無水イタコン酸などの酸無水物；塩化ビニル、塩化ビニリデン、クロロプレンなどの塩素含有単量体；ヒドロキシエチルビニルエーテル、ヒドロキシプロピルビニルエーテルなどの水酸基含有アルキルビニルエーテル；エチレングリコールモノアリルエーテル、プロピレングリコールモノアリルエーテルジエチレングリコールモノアリルエーテルなどのアルキレングリコールモノアリルエーテル；エチレン、プロピレン、イソブチレンなどのα−オレフィン；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニルなどのビニルエステル；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、シクロヘキシルビニルエーテルなどのビニルエーテル；エチルアリルエーテル、ブチルアリルエーテルなどのアリルエーテル等を例示できる。 Other monomers that can be copolymerized with acrylic monomers include aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene, and vinyl toluene; maleic acid, itaconic acid, crotonic acid, fumaric acid Acid, citraconic acid and other 瘁 C 竅 | ethylenically unsaturated carboxylic acids; sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl chloride, Chlorine-containing monomers such as vinylidene chloride and chloroprene; hydroxyl-containing alkyl vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether; alkylene glycol mono such as ethylene glycol monoallyl ether and propylene glycol monoallyl ether diethylene glycol monoallyl ether Α-olefins such as ethylene, propylene and isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; ethyl allyl ether; Examples include allyl ethers such as butyl allyl ether.
上記（ｂ）アクリル樹脂は、例えば、乳化重合法によって得られる。乳化重合の方法に関しては特に制限はなく、従来公知の方法で、水性媒体中で前記の単量体、連鎖移動剤、界面活性剤、ラジカル重合開始剤および、必要に応じて用いられる他の添加剤成分を基本組成成分とする分散系において、単量体を重合させてアクリル樹脂エマルジョンを製造することができる。 The (b) acrylic resin is obtained by, for example, an emulsion polymerization method. There is no particular limitation on the method of emulsion polymerization, and the above-mentioned monomers, chain transfer agents, surfactants, radical polymerization initiators and other additions used as necessary in an aqueous medium by a conventionally known method In a dispersion system having an agent component as a basic composition component, an acrylic resin emulsion can be produced by polymerizing monomers.
（ｂ）アクリル樹脂は、（ａ）〜（ｄ）成分中、固形分換算で、１０〜３０重量％、好ましくは２５〜３０重量％である。１０重量％未満では、得られる塗膜が固くなりバリバリの状態となりやすく、一方３０重量％を超えると、塗膜は柔らかいが、相対的にタングステン粉末の量が減ってしまい、放射線遮蔽能が低下する。 (B) Acrylic resin is 10-30 weight% in conversion of solid content in component (a)-(d), Preferably it is 25-30 weight%. If it is less than 10% by weight, the resulting coating film becomes hard and tends to be in a crumbly state. On the other hand, if it exceeds 30% by weight, the coating film is soft, but the amount of tungsten powder is relatively reduced, and the radiation shielding ability is lowered. To do.
＜（ｃ）親水性有機溶剤＞
本発明において使用する（ｃ）親水性有機溶剤は、上記（ｂ）アクリル樹脂を溶解しかつ水と相溶する有機溶剤であり、（ｂ）アクリル樹脂の溶解用以外にコーティング用組成物の固形分濃度および粘度の調整剤、さらに（ａ）オルガノアルコキシシランの加水分解調整剤として使用する。ここでの（ｃ）親水性有機溶剤は、（ａ）成分を構成するオルガノアルコキシシランの加水分解で生成するアルコールも含む。
<(C) Hydrophilic organic solvent>
The (c) hydrophilic organic solvent used in the present invention is an organic solvent that dissolves the (b) acrylic resin and is compatible with water. (B) In addition to dissolving the acrylic resin, the coating composition is solid. It is used as a partial concentration and viscosity regulator, and (a) a hydrolysis regulator of organoalkoxysilane. The (c) hydrophilic organic solvent here also includes an alcohol produced by hydrolysis of the organoalkoxysilane constituting the component (a).
本発明で使用する（ｃ）親水性有機溶剤は、アルコール類、グリコール類、エステル類、エーテル類、ケトン類などである。アルコール類としては、炭素数１〜８の脂肪族アルコール、例えばメタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔ−ブタノール、ｎ−ペンタノール、ｎ−ヘキサノール、４−メチル−２−ペンタノール、４−メチル−ｎ−ペンタノールなどが挙げられる。グリコール類としては、例えばエチレングリコール、プロピレングリコールが挙られる。エステル類としては、前記アルコール類およびグリコール類のギ酸、酢酸、プロピオン酸などのエステル、具体的にはギ酸メチル、ギ酸エチル、ギ酸ブチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸エチルなどを例示できる。 Examples of the hydrophilic organic solvent (c) used in the present invention include alcohols, glycols, esters, ethers, and ketones. Examples of alcohols include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-pentanol, n-hexanol, 4 -Methyl-2-pentanol, 4-methyl-n-pentanol and the like. Examples of glycols include ethylene glycol and propylene glycol. Examples of the esters include esters of the above alcohols and glycols such as formic acid, acetic acid, propionic acid, specifically methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, etc. it can.
エーテル類として、前記アルコール類およびグリコール類のアルキルエーテルなど、具体的にはジメチルエーテル、ジエチルエーテル、ジブチルエーテル、メチルエチルエーテル、エチルブチルエーテル、エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテル、プロピレングリコールモノエチルエーテルなどが挙げられる。ケトン類としては、アセトン、ジエチルケトン、メチルエチルケトン、アセトフェノンなどが挙げられる。 Examples of ethers include alkyl ethers of the above alcohols and glycols, specifically dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, ethyl butyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl Examples include ether. Examples of ketones include acetone, diethyl ketone, methyl ethyl ketone, and acetophenone.
（ａ）〜（ｄ）成分中の（ｃ）親水性有機溶剤の配合割合は、１０〜６０重量％、好ましくは１０〜２０重量％である。（ｃ）成分の配合割合が、１０重量％未満ではコーティング組成物の粘度が上昇しすぎ、保存安定性が低下し、一方６０重量％を超えると保存安定性は向上するもののコーティング組成物中の固形分濃度が小さくなり得られる塗膜の乾燥速度および加水分解速度が低下し、硬化に長時間を要するので好ましくない。 The blending ratio of the (c) hydrophilic organic solvent in the components (a) to (d) is 10 to 60% by weight, preferably 10 to 20% by weight. When the blending ratio of the component (c) is less than 10% by weight, the viscosity of the coating composition is excessively increased and the storage stability is lowered. On the other hand, when it exceeds 60% by weight, the storage stability is improved. Since the drying rate and hydrolysis rate of the coating film that can be obtained by reducing the solid content concentration are decreased, and it takes a long time for curing, it is not preferable.
＜（ｄ）水＞
本発明において、（ｄ）水は、（ａ）成分のオルガノアルコキシシランの加水分解剤として必須の成分である。この水としては、水道水、蒸留水、イオン交換水を使用できる。また、（ａ）成分のアルキルアルコキシシランの加水分解により生成する水も包含される。
（ａ）〜（ｄ）成分中の水の配合割合は、（ａ）〜（ｄ）成分中に１０〜７０重量％、好ましくは６０〜７０重量％である。（ｄ）成分の配合割合が、１０重量％未満では、（ａ）オルガノアルコキシシランの加水分解が十分に生起し難く、一方７０重量％を超えるとコーティング組成物の安定性が低下し、また塗膜の乾燥速度が低下するので好ましくない。
<(D) Water>
In the present invention, (d) water is an essential component as a hydrolyzing agent for organoalkoxysilane as component (a). As this water, tap water, distilled water, or ion exchange water can be used. Moreover, the water produced | generated by the hydrolysis of the alkyl alkoxysilane of (a) component is also included.
The mixing ratio of water in the components (a) to (d) is 10 to 70% by weight, preferably 60 to 70% by weight in the components (a) to (d). When the blending ratio of component (d) is less than 10% by weight, (a) organoalkoxysilane is hardly hydrolyzed. On the other hand, when it exceeds 70% by weight, the stability of the coating composition decreases. This is not preferable because the drying speed of the film is lowered.
＜（ｅ）タングステン粉末＞
（ｅ）タングステン粉末は、本発明のコーティング組成物において、この組成物から得られるシートの放射線遮蔽性を発現するために使用されるものである。
（ｅ）タングステン粉末は、通常、酸化物の水素還元によってつくられる。一般の粉末冶金には粒度が2〜5μmのタングステン粉が用いられるが、本発明においては、好ましくは３〜１０μｍである。用途によりサブミクロンの微粉末から、10μm以上の粗粉までつくることができる。タングステン粉末の粒子径は用いる酸化物の大きさや還元条件により決まる。粒子は比較的丸い形状をしており、しばしば数個の粒子がつながった二次粒子を形成している。ドーブタングステン粉末では、結晶面の発達したサイコロ状の粒子も観察される。通常の紛末の比表面積は約１ｍ２／ｇとあまり大きくない。粉末の見掛密度は2〜3Ｍｇ／ｍ３で、粒子径の大きくなるほど見掛密度は大きくなる。圧力150MPaにおける圧粉体密度は9〜10.5Ｍｇ／ｍ３で、やはり粒子径の大きくなるほど密度は大きくなる。タングステン粉末は、剛体粒子で成形性が悪く圧粉体の強度は小さい。一般に流動性は悪いが粒子径が大きくなると流動性がやや改善される。粉末は加熱により着火することがある。また長時間放置すると表面が酸化するので、窒素中または真空中で保管するのが望ましい。
本発明に用いられる（ｅ）タングステン粉末の粒度は、通常、３〜１０μｍ、好ましくは３〜５μｍ、最も好ましくは３．５μｍ前後である。
<(E) Tungsten powder>
(E) Tungsten powder is used in the coating composition of the present invention to develop the radiation shielding property of a sheet obtained from this composition.
(E) Tungsten powder is usually made by hydrogen reduction of an oxide. In general powder metallurgy, a tungsten powder having a particle size of 2 to 5 μm is used. In the present invention, it is preferably 3 to 10 μm. Depending on the application, it can be made from fine powder of submicron to coarse powder of 10μm or more. The particle size of the tungsten powder is determined by the size of the oxide used and the reduction conditions. The particles have a relatively round shape and often form secondary particles in which several particles are connected. In the dove tungsten powder, dice-like particles with a developed crystal plane are also observed. The specific surface area of ordinary powder is not so large as about 1 m 2 / g. The apparent density of the powder is 2 to 3 Mg / m 3 , and the apparent density increases as the particle diameter increases. The green compact density at a pressure of 150 MPa is 9 to 10.5 Mg / m 3. The density increases as the particle diameter increases. Tungsten powder is a rigid particle, has poor moldability, and the strength of the green compact is small. In general, the fluidity is poor, but the fluidity is slightly improved as the particle size increases. The powder may be ignited by heating. Moreover, since the surface is oxidized when left for a long time, it is desirable to store in nitrogen or in vacuum.
The particle size of the (e) tungsten powder used in the present invention is usually 3 to 10 μm, preferably 3 to 5 μm, and most preferably around 3.5 μm.
このように、タングステン粉末は、密度が高いのでそれ自体が放射線遮蔽性を有する物質である。（ｅ）タングステン粉末の配合割合は、（ａ）〜（ｄ）成分の合計量１００重量部に対し、１００〜２００重量部、好ましくは１３０〜１６０重量部、最も好ましくは１５０重量部程度である。１００重量部未満では、得られるシートの放射線遮蔽性に劣り、一方２００重量部を超えると、比重が高くなり重くなり、また価格が上昇して経済的ではない。 Thus, the tungsten powder is a substance having a radiation shielding property because of its high density. (E) The blending ratio of the tungsten powder is 100 to 200 parts by weight, preferably 130 to 160 parts by weight, and most preferably about 150 parts by weight with respect to 100 parts by weight of the total amount of the components (a) to (d). . If it is less than 100 parts by weight, the radiation shielding property of the resulting sheet is inferior. On the other hand, if it exceeds 200 parts by weight, the specific gravity increases and becomes heavy, and the price increases, which is not economical.
なお、本発明のコーティング組成物には、（ｃ）タングステン粉末以外のその他の充填材を配合することもできる。
これらの他の充填材としては、例えば有機顔料もしくは無機顔料などの非水溶性の一般的な顔料または顔料以外の粒子状もしくは繊維状の金属および合金ならびにこれらの酸化物、水酸化物、炭化物、窒化物、硫化物の１種または２種以上のものである。具体的には鉄、銅、アルミニウム、ニッケル、銀、亜鉛、フェライト、カーボンブラック、ステンレス鋼、二酸化ケイ素、酸化チタン、酸化アルミニウム、酸化クロム、酸化マンガン、酸化鉄、酸化ジルコニウム、酸化コバルト、合成ムライト、ジルコン（ケイ酸ジルコニウム）、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、二硫化モリブデン、酸化亜鉛、酸化コバルト、酸化銅、酸化ニッケル、酸化スズ、酸化セリウム、酸化バリウム、酸化アンチモン、水酸化クロム、モリブデン赤、モリブデン白、マンガンバイオレット、紺青、エメラルドグリーンなどを挙げることができるが、これらに限定されるものではない。
In addition, (c) Other fillers other than tungsten powder can also be mix | blended with the coating composition of this invention.
Examples of these other fillers include water-insoluble general pigments such as organic pigments or inorganic pigments, or particulate or fibrous metals and alloys other than pigments, and oxides, hydroxides, carbides thereof, and the like. One or more of nitrides and sulfides. Specifically, iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite , Zircon (zirconium silicate), aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, molybdenum disulfide, zinc oxide, cobalt oxide, copper oxide, nickel oxide, tin oxide, cerium oxide, barium oxide, Examples thereof include, but are not limited to, antimony oxide, chromium hydroxide, molybdenum red, molybdenum white, manganese violet, bitumen, and emerald green.
また、本発明の組成物中には、上記のように、酸を添加することが好ましい。（ｆ）酸は、組成物のｐＨを７未満の酸性領域に調整し、（ａ）成分の加水分解を促進するとともにコーティング後の塗膜の硬化促進の働きをするものである。かかる（ｆ）酸としては、硝酸、塩酸などの無機酸、酢酸、ギ酸、プロピオン酸、マレイン酸、クロロ酢酸、クエン酸、安息香酸、ジメチルマロン酸、グルタル酸、グリコール酸、マロン酸、トルエンスルホン酸、シュウ酸などの有機酸を挙げることができる。これらの酸のうち、特に酢酸が好ましい。これらの酸は、１種または２種以上を併用することができる。 Moreover, it is preferable to add an acid to the composition of the present invention as described above. (F) The acid adjusts the pH of the composition to an acidic region of less than 7, promotes hydrolysis of the component (a) and promotes curing of the coated film after coating. Examples of the acid (f) include inorganic acids such as nitric acid and hydrochloric acid, acetic acid, formic acid, propionic acid, maleic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, glutaric acid, glycolic acid, malonic acid, and toluenesulfone. Examples thereof include organic acids such as acid and oxalic acid. Of these acids, acetic acid is particularly preferred. These acids can be used alone or in combination of two or more.
かかる（ｆ）酸の組成物中の配合割合は、（ａ）〜（ｄ）成分中、（ａ）成分を構成するオルガノアルコキシシランに対し、０．１〜１重量％程度である。これにより、組成物のｐＨを７未満、好ましくは３．５〜５．５に調整することが可能となる。（ｆ）酸の含有量が、０．１重量％未満では（ａ）オルガノアルコキシシランの加水分解およびコーティング後の塗膜の硬化が充分でなくなり、一方１重量％を超えると塗膜になったとき残存酸が多くなり好ましくない。 The blending ratio of the (f) acid in the composition is about 0.1 to 1% by weight with respect to the organoalkoxysilane constituting the component (a) in the components (a) to (d). This makes it possible to adjust the pH of the composition to less than 7, preferably 3.5 to 5.5. (F) When the acid content is less than 0.1% by weight, (a) hydrolysis of the organoalkoxysilane and curing of the coated film after coating are not sufficient, while when it exceeds 1% by weight, a coating film is formed. Sometimes the residual acid increases, which is not preferable.
さらに、本発明の組成物には、各種界面活性剤、シランカップリング剤、チタンカップリング剤、金属アセチルアセトネート、またナフテン酸、オクチル酸、亜硝酸、亜硫酸、アルミン酸、炭酸などのアルカリ金属塩、チヌビン（チバ・スペシャルティ・ケミカルズ社製）などの安定剤などの従来公知のその他の添加剤を添加することもできる。 Further, the composition of the present invention includes various surfactants, silane coupling agents, titanium coupling agents, metal acetylacetonates, and alkali metals such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid. Other conventionally known additives such as a stabilizer such as salt and tinuvin (manufactured by Ciba Specialty Chemicals) can also be added.
本発明のコーティング組成物は、前記成分（ａ）〜（ｅ）および必要に応じて（ｆ）酸などの添加剤を含み、そのｐＨ７未満の酸性領域での固形分濃度が１０〜４０重量％、好ましくは１０〜３０重量％のエマルジョンあるいはコロイダル状の液状組成物である。固形分が１０重量％未満では、１回の塗布で十分な厚さの塗膜が得られず作業性が悪化したり、塗膜強度が低すぎたりし、一方４０重量％を超えるとゲル化し易く粘度が上昇し、密着性が悪化し、さらには均一な膜厚の塗膜が得られ難くなり好ましくない。 The coating composition of the present invention contains the components (a) to (e) and, if necessary, (f) an additive such as an acid, and has a solid content concentration of 10 to 40% by weight in an acidic region below pH 7. A 10 to 30% by weight emulsion or a colloidal liquid composition is preferred. If the solid content is less than 10% by weight, a coating with a sufficient thickness cannot be obtained by one application, and workability deteriorates or the coating strength is too low. On the other hand, if it exceeds 40% by weight, gelation occurs. It is not preferable because the viscosity is easily increased, the adhesion is deteriorated, and a coating film having a uniform film thickness is hardly obtained.
本発明のコーティング組成物は、例えば溶液系、あるいはエマルジョン系もしくはコロイド状の（ａ）成分（親水性有機溶剤や水を含む）に、エマルジョン系の（ｂ）アクリル樹脂（親水性有機溶剤および水を含む）を加え、さらに（ｅ）タングステン粉末と必要に応じて（ｆ）成分を加え、ロールミル、ボールミル、攪拌機などを用いて十分に分散させて調製することができるが、この調製方法に限定されるものではない。
本発明のコーティング組成物の調製方法では、(ａ)成分の混合液（具体例としては、ジアルキルジアルコキシシランの縮合物であるシリコーンオリゴマーとアルキルトリアルコキシシランの縮合物を親水性有機溶剤にとかした溶液（必要に応じて、加水分解触媒を添加）と、アクリル樹脂エマルジョン（水および親水性有機溶剤を含む）とを混合して、エマルジョン組成物を調製し、これにタングステン粉末を加えて、ロールミル、ホールミル、撹拌機などで十分に分散させることが望ましい。
The coating composition of the present invention comprises, for example, solution-based, emulsion-based or colloidal component (a) (including a hydrophilic organic solvent and water) and emulsion-based (b) acrylic resin (hydrophilic organic solvent and water). In addition, (e) tungsten powder and, if necessary, (f) component can be added and sufficiently dispersed using a roll mill, ball mill, stirrer, etc., but this method is limited. Is not to be done.
In the method for preparing the coating composition of the present invention, the mixture of component (a) (specifically, a condensate of a dialkyldialkoxysilane, a silicone oligomer and an alkyltrialkoxysilane, is dissolved in a hydrophilic organic solvent. Prepared solution (adding a hydrolysis catalyst if necessary) and acrylic resin emulsion (including water and hydrophilic organic solvent) to prepare an emulsion composition, to which tungsten powder is added, It is desirable to sufficiently disperse with a roll mill, a hall mill, a stirrer or the like.
＜基材＞
本発明のコーティング組成物のコーティングの対象となる基材は、編物、織物、不織布、紙などの布帛や、フィルム、シートなどが挙げられる。具体的には、ポリアミド繊維やポリエステル繊維、レーヨン繊維、綿、パルプなどからなる布帛類やフィルムのほか、和紙、コピー紙、タイペック（デュポン社製のポリエチレン製不織布）、壁紙、襖紙、障子紙、天井紙、テーブルクロス、カーテン、マット、ゴムシートなどが挙げられる。
<Base material>
Examples of the substrate to be coated with the coating composition of the present invention include fabrics such as knitted fabrics, woven fabrics, nonwoven fabrics, and papers, films, and sheets. Specifically, in addition to fabrics and films made of polyamide fiber, polyester fiber, rayon fiber, cotton, pulp, etc., Japanese paper, copy paper, Typek (polyethylene non-woven fabric manufactured by DuPont), wallpaper, screen paper, shoji paper , Ceiling paper, table cloth, curtain, mat, rubber sheet and the like.
基材へのコーティング組成物のコーティングには、刷毛塗り、スプレー、ディッピング、ロールコート、印刷などの塗装手段を用いることができる。１回塗りで目的とする乾燥膜厚の塗膜を形成することができ、さらに２〜５回程度塗り重ねることもできる。また、重ね塗りの場合、１回毎に加熱・乾燥処理を行ってもよい。 Coating means such as brushing, spraying, dipping, roll coating and printing can be used for coating the coating composition on the substrate. A coating film having a desired dry film thickness can be formed by a single coating, and can be further repeated about 2 to 5 times. In the case of overcoating, heating and drying treatment may be performed once.
本発明のコーティング組成物は、基材にコーティングされると、常温〜６０℃の温度で（ａ）オルガノアルコキシシランの加水分解と同時に重縮合反応を生起してゾルを生成し、さらに反応が進行してゲル、すなわちオルガノポリシロキサンとなる。これを常温で１〜６日間放置するかもしくは８０〜１５０℃で１０〜６０分間加熱することにより、溶剤の揮散とともにオルガノポリシロキサンと（ｂ）アクリル樹脂とが共縮合し、さらに（ｃ）タングステン粉末の複合した硬化塗膜を形成する。ただし、前記反応温度および放置または加熱時間は、使用する各成分の種類および配合割合により異なるので、前記に限定されるものではない。 When the coating composition of the present invention is coated on a base material, a polycondensation reaction occurs simultaneously with hydrolysis of (a) organoalkoxysilane at a temperature of room temperature to 60 ° C. to form a sol, and the reaction further proceeds It becomes a gel, that is, organopolysiloxane. By leaving this at room temperature for 1 to 6 days or heating at 80 to 150 ° C. for 10 to 60 minutes, the organopolysiloxane and (b) acrylic resin co-condensate with the volatilization of the solvent, and (c) tungsten A composite coating of powder is formed. However, the reaction temperature and the standing time or the heating time are not limited to the above, since they vary depending on the type and mixing ratio of each component used.
＜放射線遮蔽シート＞
本発明により得られる放射線遮蔽シートは、通常、基材上に本発明のコーティング組成物から形成される塗膜の複合膜であり、塗膜の目付は、通常、２．５〜７０ｋｇ／ｍ２、好ましくは１０〜５０ｇ／ｍ２，乾燥膜厚で１５０〜１，０００μｍ、好ましくは５００〜７００μｍである。少なすぎると、放射線遮蔽性に劣り、一方多すぎると、重くなるうえ、価格が上昇して経済的ではない。
<Radiation shielding sheet>
The radiation shielding sheet obtained by the present invention is usually a composite film of a coating film formed from the coating composition of the present invention on a substrate, and the basis weight of the coating film is usually 2.5 to 70 kg / m 2. , Preferably 10 to 50 g / m 2 , 150 to 1,000 μm, preferably 500 to 700 μm in terms of dry film thickness. If the amount is too small, the radiation shielding property is inferior. On the other hand, if the amount is too large, the weight increases and the price increases, which is not economical.
本発明のコーティング組成物により形成される塗膜は、オルガノポリシロキサンとアクリル樹脂の両方が有機質基材に対しては密着性を発揮することにより、各種基材への密着性が極めて優れている。
また、得られる塗膜は、オルガノポリシロキサンとアクリル樹脂とタングステン粉末の複合化により、軟らかく、耐屈曲性に優れ、はさみで容易に切断することができる。
また、本発明の基材＋塗膜からなるシートは、塗膜中に含まれるタングステン粉末により、放射線遮蔽性に極めて優れている。
The coating film formed by the coating composition of the present invention is extremely excellent in adhesion to various substrates because both organopolysiloxane and acrylic resin exhibit adhesion to organic substrates. .
Moreover, the coating film obtained is soft, excellent in bending resistance, and can be easily cut with scissors by combining organopolysiloxane, acrylic resin and tungsten powder.
Moreover, the sheet | seat which consists of a base material + coating film of this invention is very excellent in radiation shielding property by the tungsten powder contained in a coating film.
また、本発明のシートは、複合膜形成後、基材を除去することにより、塗膜単独の軟らかく、可撓性にすぐれた単独シートを形成することができる。基材を除去するには、基材が和紙の場合は、例えば複合膜の基材部分を水中で擦過して基材を剥離すればよい。 Moreover, the sheet | seat of this invention can form the single sheet | seat excellent in the softness of the coating film itself softly by removing a base material after composite film formation. In order to remove the base material, when the base material is Japanese paper, for example, the base material portion of the composite film may be rubbed in water to peel off the base material.
以下、実施例を挙げて、本発明をさらに具体的に説明する。
なお、実施例において、γ線、Ｘ線の遮蔽率は、下記のようにして測定した。
＜γ線遮蔽率＞
床から１ｍの高さで、線源と検出器測定中心までの距離を２５ｃｍとし、その間に試料がない場合とある場合の線量率について、それぞれ１０回測定した平均値からバックグラウンドの線量率を差し引いた値より、遮蔽率を求めた。
線源；セシウム１３７線源
測定器：ＮａＩシンチレーションサーベイメーターアロカＴＣＳ−１７１Ｂ
Hereinafter, the present invention will be described more specifically with reference to examples.
In the examples, the shielding rate of γ rays and X rays was measured as follows.
<Γ-ray shielding factor>
The distance from the source to the detector measurement center at a height of 1 m from the floor is 25 cm, and the dose rate of the background from the average value measured 10 times for each case with and without the sample in between. The shielding rate was calculated from the subtracted value.
Radiation source: Cesium 137 radiation source Measuring instrument: NaI scintillation survey meter Aroka TCS-171B
＜Ｘ線遮蔽率＞
フォトイオナイザー「Ｌ９４９０」（浜松ホトニクス (株)製）をＸ線源（Ｘ線エネルギー９．５ｋｅＶ、プライマリ線量１５ｍＳｖ／ｈ）とし、サンプルを透過するＸ線量を、１ｍ離れた位置に設置したサーベイメーター「Ｖｉｃｔｏｒｅｅｎ４５１Ｂ」（Global Calibration Laboratory社製）で読み取り、下記のようにしてＸ線遮蔽率を算出した。
遮蔽率=(1-X1/X2)×100(%)
X1：サンプルをおいた場合の透過X線量
X2：何もおかない場合の透過X線量
<X-ray shielding rate>
Photometer “L9490” (manufactured by Hamamatsu Photonics Co., Ltd.) was used as an X-ray source (X-ray energy 9.5 keV, primary dose 15 mSv / h), and a survey meter installed at a position 1 m away from the X-ray transmitted through the sample Reading was performed with “Victree 451B” (manufactured by Global Calibration Laboratory), and the X-ray shielding rate was calculated as follows.
Shielding rate = (1-X1 / X2) x 100 (%)
X1: Transmitted X-ray dose with sample
X2: Transmitted X-ray dose when there is nothing
参考例１（ＲＡＳ２０１の調製）
下記配合処方により、ＳＰＫ−９０２Ｂ ２０重量部、ＫＥ−２５６ ６７重量部、イソプロピルアルコール １３重量部を混合して撹拌し、エマルジョン系のＲＡ２０１を調製した。
ＲＡＳ２０１配合処方
ＳＰＫ−９０２Ｂ ２０重量部
ＫＥ−２５６ ６７重量部
イソプロピルアルコール １３重量部
ここで、ＳＰＫ−９０２Ｂは、混合液［シリコーンオリゴマー（ジメチルジメトキシシランを加水分解してなるオリゴマーで３〜４量体）３０重量％と、ポリアルキルアルコキシシラン（メチルトリメトキシシランの加水分解・縮合物）７０重量％の混合物］３０重量％に、ＴＰＴ（加水分解触媒としてテトラプロポキシチタン）を全オルガノアルコキシシランに対し１重量％、および親水性有機溶剤としてイソプロピルアルコール７０重量％含む透明な溶剤系で、固形分濃度は３５重量％であり、本発明の（ａ）成分に相当する。
また、ＫＥ−２５６は、アクリル樹脂［（メタ）アクリル酸エステル系共重合体］３０重量％、イソプロピルアルコール７重量％、水６０重量％、トリエタノールアミン３重量％からなる、アクリル樹脂エマルジョンである。
Reference Example 1 (Preparation of RAS201)
According to the following formulation, 20 parts by weight of SPK-902B, 67 parts by weight of KE-256, and 13 parts by weight of isopropyl alcohol were mixed and stirred to prepare an emulsion-based RA201.
RAS201 blended formulation SPK-902B 20 parts by weight KE-256 67 parts by weight Isopropyl alcohol 13 parts by weight Here, SPK-902B is a mixed solution [silicone oligomer (an oligomer formed by hydrolyzing dimethyldimethoxysilane, which is a 3- to 4-mer. ) 30% by weight and polyalkylalkoxysilane (methyltrimethoxysilane hydrolysis / condensate) 70% by weight mixture] 30% by weight, TPT (tetrapropoxytitanium as hydrolysis catalyst) to all organoalkoxysilanes It is a transparent solvent system containing 1% by weight and 70% by weight of isopropyl alcohol as a hydrophilic organic solvent. The solid concentration is 35% by weight and corresponds to the component (a) of the present invention.
KE-256 is an acrylic resin emulsion comprising 30% by weight of an acrylic resin [(meth) acrylic ester copolymer], 7% by weight of isopropyl alcohol, 60% by weight of water, and 3% by weight of triethanolamine. .
参考例２（ＲＡＳ２０２の調製）
下記配合処方により、ＳＰＫ−９０２Ｂ ２０重量部、ＫＥ−２５６ ６７重量部、イソプロピルアルコール ７重量部、イソプロピルアルコール７重量部、チヌビン３８４−２（チバ・スペシャルティ・ケミカルズ社製、安定剤）６重量部を混合して撹拌し、エマルジョン状態のＲＡＳ２０２を調製した。
ＲＡＳ２０２配合処方
ＳＰＫ−９０２Ｂ ２０重量部
ＫＥ−２５６ ６７重量部
イソプロピルアルコール ７重量部
チヌビン ６重量部
Reference Example 2 (Preparation of RAS202)
According to the following formulation, SPK-902B 20 parts by weight, KE-256 67 parts by weight, isopropyl alcohol 7 parts by weight, isopropyl alcohol 7 parts by weight, Tinuvin 384-2 (manufactured by Ciba Specialty Chemicals, stabilizer) 6 parts by weight Were mixed and stirred to prepare RAS202 in an emulsion state.
RAS202 prescription SPK-902B 20 parts by weight KE-256 67 parts by weight Isopropyl alcohol 7 parts by weight Tinuvin 6 parts by weight
実施例１（ＲＡＳ２０１を用いたγ線遮蔽効果）
参考例１で調製されたＲＡＳ２０１を用い、これに重量が１．５重量倍のタングステン粉末（東邦金属株式会社製、粒度；３．５μｍ）を加えて、固形分濃度が３５重量％のコーティング組成物を調製し、これを、クラフト紙（王子製紙社製、坪量；７０ｇ／ｍ２、）にローラを用いてコーティングし、常温で１時間乾燥して、本発明のシートを作成した。このものは、柔軟であり、はさみで容易に切断することができた。
これをタテ・ヨコが２２ｃｍ×２２ｃｍの試験片に切り出し、５枚、あるいは１０枚を重ねて、ガンマ線の遮蔽率を調べた。結果を表１に示す。
Example 1 (γ-ray shielding effect using RAS201)
Using RAS201 prepared in Reference Example 1, a 1.5 times weight weight tungsten powder (manufactured by Toho Metal Co., Ltd., particle size: 3.5 μm) was added thereto, and the solid content concentration was 35% by weight. A product was prepared, and this was coated on kraft paper (manufactured by Oji Paper Co., Ltd., basis weight; 70 g / m 2 ) using a roller, and dried at room temperature for 1 hour to prepare a sheet of the present invention. This was flexible and could be easily cut with scissors.
This was cut into a test piece of 22 cm × 22 cm by vertical and horizontal, 5 or 10 sheets were stacked, and the shielding rate of gamma rays was examined. The results are shown in Table 1.
実施例２（ＲＡＳ２０２を用いたγ線遮蔽効果）
参考例２で調製されたＲＡＳ２０２を用い、これに重量が１．５重量倍のタングステン粉末（東邦金属株式会社製、粒度；３．５μｍ）を加えて、固形分濃度が３５重量％のコーティング組成物を調製し、これを、クラフト紙（王子製紙社製、坪量；７０ｇ／ｍ２、）にハケを用いてコーティングし、常温で１時間乾燥して、本発明のシートを得た。これらのものは、柔軟であり、はさみで容易に切断することができた。
これらをタテヨコが２２ｃｍ×２２ｃｍの試験片に切り出し、３０枚重ね、１０枚重ね、あるいは１枚単独（上段）、さらに同じシートを用いて、１枚単独、２枚重ね、３枚重ね（下段）の場合のγ線の遮蔽率を調べた。結果を表１に示す。
Example 2 (γ-ray shielding effect using RAS202)
Using RAS202 prepared in Reference Example 2, a tungsten powder having a weight of 1.5 times by weight (manufactured by Toho Metals Co., Ltd., particle size: 3.5 μm) was added thereto, and the coating composition had a solid content concentration of 35% by weight. A product was prepared, and this was coated on kraft paper (manufactured by Oji Paper Co., Ltd., basis weight; 70 g / m 2 ) using a brush and dried at room temperature for 1 hour to obtain a sheet of the present invention. These were flexible and could be easily cut with scissors.
Cut these into 22cm x 22cm test pieces, stacked 30 sheets, 10 sheets, or 1 sheet alone (upper), and using the same sheet, 1 sheet alone, 2 sheets stacked, 3 sheets stacked (lower stage) In this case, the shielding rate of γ rays was examined. The results are shown in Table 1.
表１から、次のようなことが分かる。
実施例１から、１枚あたりの塗布量が同じ場合には、試験片の枚数に比例してγ線の遮蔽効果が向上することが分かる。
実施例２から、３０枚重ね、１０枚重ね、１枚単独でも（上段）、また、塗布量が同じシートを１枚単独、2枚重ね、3枚重ねすると（下段）、枚数（すなわち、塗布量）に比例して、γ線遮蔽効果が向上することが分かる。これらから、結果的には塗布量に比例してγ線の遮蔽効果が表れることが分かる。実施例１〜２から、本発明の放射線遮蔽シートは、γ線の遮蔽効果に優れていることが分かる。
Table 1 shows the following.
From Example 1, it can be seen that when the coating amount per sheet is the same, the gamma ray shielding effect is improved in proportion to the number of test pieces.
From Example 2, 30 sheets, 10 sheets, 1 sheet alone (upper stage), and 1 sheet alone, 2 sheets, 3 sheets (lower stage) with the same coating amount, the number of sheets (ie, coating) It can be seen that the gamma ray shielding effect improves in proportion to the amount. From these results, it can be seen that the effect of shielding γ rays appears in proportion to the coating amount. From Examples 1-2, it can be seen that the radiation shielding sheet of the present invention is excellent in the shielding effect of γ rays.
実施例３(ＲＡＳ２０２を用いたＸ線遮蔽効果)
参考例２で調製されたＲＡＳ２０２を用い、これに重量が１．５重量倍のタングステン粉末（東邦金属株式会社製、粒度；３．５μｍ）を加えて、固形分濃度が３５重量％のコーティング組成物を調製し、これを、クラフト紙（王子製紙社製、坪量；７０ｇ／ｍ２、）にハケを用いて、実施例２と同様にコーティングして、表２に示すようなシートを作成して、これをタテ・ヨコが２２ｃｍ×２２ｃｍの試験片に切り出して評価した。結果を表２に示す。
Example 3 (X-ray shielding effect using RAS202)
Using RAS202 prepared in Reference Example 2, a tungsten powder having a weight of 1.5 times by weight (manufactured by Toho Metals Co., Ltd., particle size: 3.5 μm) was added thereto, and the coating composition had a solid content concentration of 35% by weight. A sheet is prepared as shown in Table 2 by coating it with kraft paper (made by Oji Paper Co., Ltd., basis weight; 70 g / m 2 ) using a brush in the same manner as in Example 2. Then, this was cut into a 22 cm × 22 cm test piece and evaluated. The results are shown in Table 2.
表２から、次のようなことが分かる。
Ｘ線の遮蔽効果においても、塗布量に比例してＸ線遮蔽率が向上している。Ｘ線の遮蔽効果は、人体の場合、０．２５ｍｍＰｂ以上であればよいことが判明しているが、本発明の放射線遮蔽シートは、いずれもこの値をクリアしており、Ｘ線遮蔽効果に優れていることが分かる。
Table 2 shows the following.
Also in the X-ray shielding effect, the X-ray shielding rate is improved in proportion to the coating amount. The X-ray shielding effect has been found to be 0.25 mmPb or more in the case of the human body, but all of the radiation shielding sheets of the present invention have cleared this value and are effective in the X-ray shielding effect. It turns out that it is excellent.
本発明により得られる放射線遮蔽シートは、柔軟ではさみでも切断することができ、γ線、Ｘ線などの放射線を遮蔽する効果が高いので、放射線遮蔽用防護服や、放射線治療に用いられる放射線防護服などに用いられるほか、本発明の組成物をあらゆる基材に塗布することにより、放射線遮蔽性に優れた各種の用具などに用いることができる。 The radiation shielding sheet obtained by the present invention is flexible and can be cut with scissors, and has a high effect of shielding radiation such as γ-rays and X-rays. Therefore, radiation shielding protective clothing and radiation protection used for radiation therapy are used. In addition to being used for clothes and the like, the composition of the present invention can be applied to various substrates to be used for various tools having excellent radiation shielding properties.
Claims (8)
A radiation shielding sheet obtained by the production method according to claim 7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016185997A1 (en) * | 2015-05-15 | 2016-11-24 | 岩宮 陽子 | Radiation shielding sheet and method for manufacturing same |
| KR101736171B1 (en) | 2015-10-23 | 2017-05-16 | 한전원자력연료 주식회사 | Water-soluble coating composition for nuclear fuel rod protection |
| KR20230072359A (en) * | 2021-11-17 | 2023-05-24 | 계명대학교 산학협력단 | Radiation shielding fiber and Manufacturing method of the same |
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| WO2006090629A1 (en) * | 2005-02-23 | 2006-08-31 | Kabushiki Kaisha Toshiba | Radiation shielding sheet |
| WO2012017846A1 (en) * | 2010-08-06 | 2012-02-09 | Dic株式会社 | One-pack coating composition, photocatalyst employing same, coating film of same, and method for manufacturing same |
| JP3184220U (en) * | 2013-03-25 | 2013-06-20 | 株式会社超越化研 | Radiation shielding suit |
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| JPS5566799A (en) * | 1978-11-14 | 1980-05-20 | Matsushita Electric Ind Co Ltd | Flame retardant silicone composition having xxray shielding ability |
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| WO2016185997A1 (en) * | 2015-05-15 | 2016-11-24 | 岩宮 陽子 | Radiation shielding sheet and method for manufacturing same |
| KR101736171B1 (en) | 2015-10-23 | 2017-05-16 | 한전원자력연료 주식회사 | Water-soluble coating composition for nuclear fuel rod protection |
| KR20230072359A (en) * | 2021-11-17 | 2023-05-24 | 계명대학교 산학협력단 | Radiation shielding fiber and Manufacturing method of the same |
| KR102602740B1 (en) * | 2021-11-17 | 2023-11-15 | 계명대학교 산학협력단 | Radiation shielding fiber and Manufacturing method of the same |
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