JP2013230965A - Manganese dioxide and curable composition containing the same - Google Patents
Manganese dioxide and curable composition containing the same Download PDFInfo
- Publication number
- JP2013230965A JP2013230965A JP2013064564A JP2013064564A JP2013230965A JP 2013230965 A JP2013230965 A JP 2013230965A JP 2013064564 A JP2013064564 A JP 2013064564A JP 2013064564 A JP2013064564 A JP 2013064564A JP 2013230965 A JP2013230965 A JP 2013230965A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- monoclinic
- birnessite
- curable composition
- ion
- 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.)
- Granted
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011734 sodium Substances 0.000 claims abstract description 61
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 48
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 48
- 229920001021 polysulfide Polymers 0.000 claims abstract description 42
- 230000008961 swelling Effects 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000011229 interlayer Substances 0.000 claims abstract description 27
- 150000001768 cations Chemical class 0.000 claims abstract description 25
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 14
- -1 proton Chemical compound 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 7
- 229960002447 thiram Drugs 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001422 barium ion Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910001427 strontium ion Inorganic materials 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 2
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 84
- 238000003786 synthesis reaction Methods 0.000 description 84
- 239000000706 filtrate Substances 0.000 description 45
- 239000000047 product Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 16
- 239000004570 mortar (masonry) Substances 0.000 description 15
- 239000000725 suspension Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 238000007654 immersion Methods 0.000 description 12
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 5
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 5
- 239000013065 commercial product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- LXODQLXKQIJVNK-UHFFFAOYSA-N 2-(2-benzoyloxypropoxy)propyl benzoate Chemical class C=1C=CC=CC=1C(=O)OC(C)COC(C)COC(=O)C1=CC=CC=C1 LXODQLXKQIJVNK-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-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
- AHSGHEXYEABOKT-UHFFFAOYSA-N 2-[2-(2-benzoyloxyethoxy)ethoxy]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOCCOC(=O)C1=CC=CC=C1 AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
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- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- VVKREWPWSWPBGC-UHFFFAOYSA-N benzoic acid;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)COC(C)CO.OC(=O)C1=CC=CC=C1 VVKREWPWSWPBGC-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
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- 229930195729 fatty acid Natural products 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IJIVUROORPGPBF-UHFFFAOYSA-K iron(3+);trichloride;dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cl-].[Fe+3] IJIVUROORPGPBF-UHFFFAOYSA-K 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- BEYCFZBNRLPHEP-UHFFFAOYSA-L manganese(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Mn+2] BEYCFZBNRLPHEP-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- UGNANEGDDBXEAS-UHFFFAOYSA-L nickel(2+);dichloride;dihydrate Chemical compound O.O.Cl[Ni]Cl UGNANEGDDBXEAS-UHFFFAOYSA-L 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 238000011002 quantification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940047908 strontium chloride hexahydrate Drugs 0.000 description 1
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- OIBMCFORWDWZQD-UHFFFAOYSA-K trichlorolanthanum dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cl-].[La+3] OIBMCFORWDWZQD-UHFFFAOYSA-K 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
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- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、液状ポリサルファイドポリマーの硬化剤として好適に用いられる、二酸化マンガンおよびその硬化型組成物に関するものである。 The present invention relates to manganese dioxide and a curable composition thereof that are suitably used as a curing agent for a liquid polysulfide polymer.
液状ポリサルファイドポリマーの酸化剤として、アルカリ処理により活性化された二酸化マンガンが使用されている。二酸化マンガンとしては、例えば天然の二酸化マンガン鉱をアルカリ処理したものや、特許文献１に記載されたナトリウムバーネサイト構造を有する二酸化マンガンなどが用いられ、可塑剤に分散させたペースト状の硬化剤にすることが一般的である。 Manganese dioxide activated by alkali treatment is used as an oxidizing agent for liquid polysulfide polymers. As manganese dioxide, for example, natural manganese dioxide ore treated with alkali, or manganese dioxide having a sodium birnessite structure described in Patent Document 1 is used, and a paste-like curing agent dispersed in a plasticizer. It is common to make it.
液状ポリサルファイドポリマーを二酸化マンガンからなる硬化剤で硬化して得られるゴム状の硬化物は、分子の主鎖に硫黄を含んでおり、また二重結合を含まないことから、耐油性、耐候性、水密性、気密性に優れた特徴を持ち、さらに接着性も良好である。このため液状ポリサルファイドポリマーの硬化物は、シーリング材、接着剤および塗料として広く用いられている。特に複層ガラス用途においては、シリコーン系シーリング材などの他基材に勝る、硬化性のよさ、水密性や気密性のよさから古くから用いられている。しかしながら、二酸化マンガンからなる硬化剤で硬化させたポリサルファイドポリマーの硬化物は、他基材に比べて、加速耐久性試験における温水浸漬時の膨潤や強度低下が大きい場合があった。 A rubber-like cured product obtained by curing a liquid polysulfide polymer with a curing agent made of manganese dioxide contains sulfur in the main chain of the molecule and does not contain a double bond, so oil resistance, weather resistance, It has excellent watertightness and airtightness characteristics, and also has good adhesion. Therefore, a cured product of a liquid polysulfide polymer is widely used as a sealing material, an adhesive and a paint. In particular, in multilayer glass applications, it has been used for a long time because of its excellent curability, watertightness and airtightness, which is superior to other base materials such as silicone sealants. However, a cured product of a polysulfide polymer cured with a curing agent made of manganese dioxide sometimes has a greater swelling or lowering of strength when immersed in warm water in an accelerated durability test than other substrates.
このため、特許文献２は、二酸化マンガンに酸処理をすることにより、これを用いた硬化物の温水浸漬時の膨潤や強度低下を抑えることを提案している。しかしながら、特許文献２に記載された酸処理をした二酸化マンガンは、その表面のアルカリは除去できるものの、ペースト状の硬化剤を調製する際、この二酸化マンガンを、三本ロールミルなどを用いて可塑剤へ分散させるときに、内部のアルカリが溶出してしまうことがあった。このため酸処理をした二酸化マンガンを用いたポリサルファイドポリマーの硬化物に長期間の温水浸漬試験を行うと、硬化物が膨潤したり強度が低下したりする場合があった。 For this reason, Patent Document 2 proposes that manganese dioxide is subjected to an acid treatment to suppress swelling and strength reduction when a cured product using the same is immersed in warm water. However, the acid-treated manganese dioxide described in Patent Document 2 can remove the alkali on the surface, but when preparing a paste-like curing agent, the manganese dioxide is used as a plasticizer using a three-roll mill or the like. In some cases, the alkali inside was eluted when it was dispersed. For this reason, when a long-term hot water immersion test was performed on a cured product of polysulfide polymer using acid-treated manganese dioxide, the cured product sometimes swelled or the strength decreased.
また、特許文献３は、二酸化マンガン以外の有機化合物を硬化剤として用いることで硬化物の温水浸漬時の膨潤や強度低下を抑えることを提案している。しかしながら、特許文献３に記載された有機化合物を用いる場合、適切な作業時間の確保、早い硬度発現、および硬化後のシーリング材の物性からなるバランスを取るためには、適切な触媒や添加剤の選択が重要であり、また適切な配合比率が遵守できない場合には性能が大きく低下することがあった。そのため、作業性が良好で実用的な二酸化マンガンを硬化剤に使用したとき、ポリサルファイドポリマーの硬化物における温水浸漬時の膨潤や強度低下を、一層抑制する改良が望まれていた。 Moreover, patent document 3 has proposed suppressing the swelling at the time of warm water immersion of a hardened | cured material, and a strength fall by using organic compounds other than manganese dioxide as a hardening | curing agent. However, in the case of using the organic compound described in Patent Document 3, in order to achieve a balance consisting of ensuring appropriate working time, rapid hardness development, and physical properties of the sealing material after curing, an appropriate catalyst or additive The selection is important, and when the proper blending ratio cannot be observed, the performance may be greatly reduced. Therefore, when a practical manganese dioxide having good workability is used as a curing agent, an improvement that further suppresses swelling and strength reduction when immersed in warm water in a cured product of polysulfide polymer has been desired.
本発明の目的は、液状ポリサルファイドポリマーを硬化させることができ、かつ、長期間温水に浸漬させても膨潤や強度低下が少ない硬化物が得られる、二酸化マンガンおよびその硬化型組成物を提供することである。 An object of the present invention is to provide manganese dioxide and a curable composition thereof, which can cure a liquid polysulfide polymer and can obtain a cured product with little swelling and reduced strength even when immersed in warm water for a long period of time. It is.
本発明の二酸化マンガンは、液状ポリサルファイドポリマーの硬化剤に使用する二酸化マンガンであって、下記式（１）
Ｎａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏ （１）
で示される単斜晶系ナトリウムバーネサイトの層間に存在するナトリウムイオンを、一価〜三価のカチオンで置換した単斜晶系カチオン置換バーネサイト型二酸化マンガンからなることを特徴とする。
The manganese dioxide of the present invention is manganese dioxide used as a curing agent for a liquid polysulfide polymer, and has the following formula (1):
Na 0.55 Mn 2 O 4 .1.5H 2 O (1)
It is characterized by comprising monoclinic cation-substituted birnessite-type manganese dioxide in which sodium ions existing between monoclinic sodium birnessite layers are substituted with monovalent to trivalent cations.
また本発明の硬化型組成物は、上記本発明の二酸化マンガンおよび液状ポリサルファイドポリマーを含有することを特徴とする。 The curable composition of the present invention is characterized by containing the manganese dioxide of the present invention and a liquid polysulfide polymer.
本発明の二酸化マンガンは、単斜晶系のバーネサイト構造を持つ活性化二酸化マンガンであり、液状ポリサルファイドポリマーを硬化させることができる。また単斜晶系のバーネサイトの層間に含まれるナトリウムイオンを吸水性がより低いカチオンに置換したので、ポリサルファイドポリマーの硬化物を長期間温水に浸漬させても膨潤や強度低下を少なくすることができる。 The manganese dioxide of the present invention is activated manganese dioxide having a monoclinic birnessite structure, and can cure a liquid polysulfide polymer. In addition, since sodium ions contained between monoclinic birnessite layers are replaced by cations with lower water absorption, swelling and strength reduction can be reduced even when the cured product of polysulfide polymer is immersed in warm water for a long period of time. .
前記カチオンとしては、カルシウムイオン、プロトン、アンモニウムイオン、マグネシウムイオン、ストロンチウムイオン、ニッケルイオン、鉄(III)イオン、ランタンイオン、亜鉛イオン、バリウムイオンから選ばれる少なくとも一つが好ましい。 The cation is preferably at least one selected from calcium ions, protons, ammonium ions, magnesium ions, strontium ions, nickel ions, iron (III) ions, lanthanum ions, zinc ions, and barium ions.
本発明の二酸化マンガンは、ナトリウム含量が０．１５重量％以下であるとよい。また単斜晶系カチオン置換バーネサイトの層間距離が６．９０〜７．２５オングストロームであるとよい。この二酸化マンガンは、前記式（１）で示される単斜晶系ナトリウムバーネサイトを、一価〜三価のカチオンを含む水溶液で処理することによりナトリウムイオンをカチオンで置換して、乾燥することにより得られる。 Manganese dioxide of the present invention preferably has a sodium content of 0.15% by weight or less. The interlayer distance of the monoclinic cation-substituted banesite is preferably 6.90 to 7.25 angstroms. This manganese dioxide is obtained by treating the monoclinic sodium birnessite represented by the above formula (1) with an aqueous solution containing monovalent to trivalent cations to replace sodium ions with cations and drying. Is obtained.
本発明の硬化型組成物は、上述した二酸化マンガンが液状ポリサルファイドポリマーを硬化させ、しかも長期間温水に浸漬させても膨潤や強度低下を少なくした硬化物を得ることができる。 The curable composition of the present invention can obtain a cured product in which the above-described manganese dioxide cures the liquid polysulfide polymer and further reduces swelling and strength reduction even when immersed in warm water for a long period of time.
上記硬化型組成物は、充填材、可塑剤、加硫促進剤から選ばれる少なくとも一つを含有することができる。充填材としてはカーボンブラック、炭酸カルシウム、シリカ、マイクロバルーンから選ばれる少なくとも一つにすることができる。可塑剤としては、フタル酸エステル、塩素化パラフィン、ジプロピレングリコールジベンゾエート、ハロゲン末端硫黄含有重合体から選ばれる少なくとも一つにすることができる。加硫促進剤は、チウラム系加硫促進剤、グアニジン系加硫促進剤から選ばれる少なくとも一つにすることができる。 The curable composition may contain at least one selected from a filler, a plasticizer, and a vulcanization accelerator. The filler can be at least one selected from carbon black, calcium carbonate, silica, and microballoons. The plasticizer can be at least one selected from phthalic acid esters, chlorinated paraffins, dipropylene glycol dibenzoates, and halogen-terminated sulfur-containing polymers. The vulcanization accelerator can be at least one selected from a thiuram vulcanization accelerator and a guanidine vulcanization accelerator.
本発明の硬化型組成物の硬化物は、８０℃温水に１０日間浸漬した後の体積膨潤率を１０％未満にすることができる。 The cured product of the curable composition of the present invention can have a volume swelling ratio of less than 10% after being immersed in warm water at 80 ° C. for 10 days.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
上述した特許文献１は、ポリサルファイドポリマーの硬化剤として使用する二酸化マンガンが、斜方晶系ナトリウムバーネサイト構造（Ｎａ4Ｍｎ14Ｏ27・９Ｈ2Ｏ）を有することを記載している。しかし、現在市販されているポリサルファイドポリマー硬化用の二酸化マンガンは、単斜晶系ナトリウムバーネサイト構造（Ｎａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏ）を有するものが知られている。この単斜晶系ナトリウムバーネサイト構造をもつ二酸化マンガンは、液状ポリサルファイドポリマーを酸化し硬化させる能力が優れている。 Patent Document 1 described above describes that manganese dioxide used as a curing agent for a polysulfide polymer has an orthorhombic sodium birnessite structure (Na 4 Mn 14 O 27 · 9H 2 O). However, currently commercially available manganese dioxide for curing polysulfide polymers is known to have a monoclinic sodium birnessite structure (Na 0.55 Mn 2 O 4 .1.5H 2 O). Manganese dioxide having this monoclinic sodium birnessite structure has an excellent ability to oxidize and cure a liquid polysulfide polymer.
本発明の二酸化マンガンは、下記式（１）
Ｎａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏ （１）
で示される単斜晶系ナトリウムバーネサイトの層間に存在するナトリウムイオンを、一価〜三価のカチオンで置換した単斜晶系カチオン置換バーネサイト型二酸化マンガンからなる。この二酸化マンガンは、単斜晶系のバーネサイト構造をもつため液状ポリサルファイドポリマーを酸化させる能力が優れる。この単斜晶系のバーネサイト構造の層間距離は、好ましくは６．７０〜７．５０オングストローム、より好ましくは６．９０〜７．２５オングストロームである。層間距離をこのような範囲にすることにより、単斜晶系のバーネサイト構造を形成することができる。
The manganese dioxide of the present invention has the following formula (1):
Na 0.55 Mn 2 O 4 .1.5H 2 O (1)
It consists of monoclinic cation-substituted birnessite-type manganese dioxide in which sodium ions existing between the layers of monoclinic sodium birnessite represented by (1) are substituted with monovalent to trivalent cations. This manganese dioxide has a monoclinic birnessite structure and therefore has an excellent ability to oxidize a liquid polysulfide polymer. The interlayer distance of this monoclinic banesite structure is preferably 6.70-7.50 angstroms, more preferably 6.90-7.25 angstroms. By setting the interlayer distance in such a range, a monoclinic birnessite structure can be formed.
前記式（１）で表わされる単斜晶系ナトリウムバーネサイトは、層間にナトリウムイオンを含み、このナトリウムイオンは吸水性が高い。このため、単斜晶系ナトリウムバーネサイト型二酸化マンガンを使用してポリサルファイドポリマーを硬化させると、初期の水密性や気密性は優れるものの、温水浸漬試験をしたとき硬化物の膨潤や強度低下が大きくなる。 The monoclinic sodium banesite represented by the formula (1) contains sodium ions between the layers, and the sodium ions have high water absorption. For this reason, when polysulfide polymer is cured using monoclinic sodium birnessite-type manganese dioxide, the initial watertightness and airtightness are excellent, but when the hot water immersion test is performed, the cured product swells and the strength decreases. growing.
本発明の二酸化マンガンは、単斜晶系のバーネサイト構造の層間にある吸水性が高いナトリウムイオンを、吸水性が低い一価〜三価のカチオンに置換したので、二酸化マンガンの吸水性を低減することができる。またこの二酸化マンガンを硬化剤にすることによりポリサルファイドポリマーの硬化物の吸水性を大幅に低減するので、長期間温水に浸漬させても膨潤や強度低下を少なくすることができる。すなわち、ポリサルファイドポリマー硬化物の長期耐久性を改良することができる。 The manganese dioxide of the present invention reduces the water absorption of manganese dioxide by replacing sodium ions with high water absorption between the layers of the monoclinic birnessite structure with monovalent to trivalent cations with low water absorption. be able to. Moreover, since the water absorption of the cured product of polysulfide polymer is greatly reduced by using this manganese dioxide as a curing agent, swelling and strength reduction can be reduced even when immersed in warm water for a long period of time. That is, the long-term durability of the polysulfide polymer cured product can be improved.
ナトリウムイオンを置換する一価〜三価のカチオンは、単斜晶系のバーネサイト構造の層間に入るイオン半径を有したもので、吸水性が低いカチオンであれば特に制限はない。好ましくは例えばカルシウムイオン、マグネシウムイオン、ストロンチウムイオン、ニッケルイオン、鉄(III)イオン、ランタンイオン、亜鉛イオン、バリウムイオン等の金属イオンや、プロトン、アンモニウムイオン等を挙げることができる。 The monovalent to trivalent cation replacing the sodium ion has an ionic radius that falls between the layers of the monoclinic birnessite structure, and is not particularly limited as long as it is a cation with low water absorption. Preferable examples include metal ions such as calcium ion, magnesium ion, strontium ion, nickel ion, iron (III) ion, lanthanum ion, zinc ion, barium ion, proton, ammonium ion and the like.
本発明において、ナトリウムイオンを一価〜三価のカチオンで置換するとは、少なくとも一価〜三価のカチオンの含量をナトリウムイオンの含量より多くすることをいう。 In the present invention, substitution of sodium ions with monovalent to trivalent cations means that at least the content of monovalent to trivalent cations is higher than the content of sodium ions.
ポリサルファイドポリマーの硬化物の長期温水浸漬時の体積膨潤率を抑制するには、低吸水性カチオンの置換率が高く、すなわち残存するナトリウムイオン量が少ない方がよい。カチオン置換した二酸化マンガンにおけるナトリウムイオンの含量は、好ましくは０．４０重量％以下、より好ましくは０．１５重量％以下にするとよい。 In order to suppress the volume swelling rate of the cured product of polysulfide polymer during long-term warm water immersion, it is preferable that the substitution rate of the low water-absorbing cation is high, that is, the amount of remaining sodium ions is small. The content of sodium ions in the cation-substituted manganese dioxide is preferably 0.40% by weight or less, more preferably 0.15% by weight or less.
本発明の二酸化マンガンは、前記式（１）で示される単斜晶系ナトリウムバーネサイトを、一価〜三価のカチオンを含む水溶液で処理しナトリウムイオンを置換することにより、一価〜三価のカチオンを単斜晶系のバーネサイトの層間に導入後、その生成物を水洗し、乾燥することにより得られる。なおナトリウムイオンを一価〜三価のカチオンで置換する方法は、上記以外に通常行われるイオン置換方法を用いることができる。 In the manganese dioxide of the present invention, monoclinic sodium birnessite represented by the above formula (1) is treated with an aqueous solution containing monovalent to trivalent cations to replace sodium ions, thereby obtaining monovalent to trivalent manganese. It is obtained by introducing a valent cation between layers of monoclinic birnessite, washing the product with water and drying. In addition, the method of substituting a sodium ion with a monovalent to trivalent cation can use the ion replacement method performed normally other than the above.
バーネサイトとしては、天然のバーネサイト鉱や、化学合成によるバーネサイトを使用し、アルカリ処理を行い活性化した単斜晶系ナトリウムバーネサイトを用いることができる。化学合成によるバーネサイトとしては、沈殿法で得られた物、すなわち、酸素の存在下、塩化マンガン、硫酸マンガン、硝酸マンガン等の水溶液に苛性ソーダ等アルカリ水溶液を滴下し、得られた物等があげられる。 As the birnessite, it is possible to use natural birnessite or monoclinic sodium birnessite activated by alkali treatment using burntite by chemical synthesis. Examples of banesite by chemical synthesis include those obtained by precipitation, that is, products obtained by dropping alkaline aqueous solution such as caustic soda into aqueous solution of manganese chloride, manganese sulfate, manganese nitrate, etc. in the presence of oxygen. .
一価〜三価のカチオンを含む水溶液は、水溶性の金属塩を含むものであれば特に限定されない。金属塩は、好ましくは塩化物、硫酸塩、硝酸塩、炭酸塩、有機酸塩であるとよい。水溶液の金属塩の濃度は、好ましくは０．５〜５０重量％、より好ましくは２〜３０重量％であるとよい。 The aqueous solution containing monovalent to trivalent cations is not particularly limited as long as it contains a water-soluble metal salt. The metal salt is preferably a chloride, sulfate, nitrate, carbonate, or organic acid salt. The concentration of the metal salt in the aqueous solution is preferably 0.5 to 50% by weight, more preferably 2 to 30% by weight.
一価〜三価のカチオンを含む水溶液での処理方法は、特に限定されないが、例えばこれらの水溶液に二酸化マンガンを添加して撹拌すればよい。水溶液への二酸化マンガンの添加量については、カチオンを含む水溶液１リットルに対して好ましくは０．１〜２００ｇ、より好ましくは０．５〜１５０ｇにするとよい。 The treatment method with an aqueous solution containing monovalent to trivalent cations is not particularly limited. For example, manganese dioxide may be added to these aqueous solutions and stirred. The amount of manganese dioxide added to the aqueous solution is preferably 0.1 to 200 g, more preferably 0.5 to 150 g, per liter of the aqueous solution containing cations.
処理条件は、水溶液の温度が好ましくは１０〜８０℃、より好ましくは２０〜５０℃で、処理時間が好ましくは１〜７２時間、より好ましくは５〜２４時間程度撹拌するとよい。 The treatment conditions are such that the temperature of the aqueous solution is preferably 10 to 80 ° C., more preferably 20 to 50 ° C., and the treatment time is preferably 1 to 72 hours, more preferably about 5 to 24 hours.
またカチオン置換した二酸化マンガンを乾燥する際の条件は、好ましくは２０〜１８０℃、より好ましくは２０〜１５０℃、更に好ましくは６０〜１５０℃、特に好ましくは６０〜１００℃にて、１〜１５０時間行われる。 The conditions for drying the cation-substituted manganese dioxide are preferably 20 to 180 ° C, more preferably 20 to 150 ° C, still more preferably 60 to 150 ° C, particularly preferably 60 to 100 ° C, and 1 to 150. Done for hours.
本発明の硬化型組成物は、単斜晶系のバーネサイト構造で吸水性が低いカチオンを含む活性化二酸化マンガンおよび液状ポリサルファイドポリマーを含有するため、硬化物の温水浸漬時の膨潤や強度低下を低減させることができる。 Since the curable composition of the present invention contains activated manganese dioxide containing a monoclinic birnessite structure and a low water-absorbing cation and a liquid polysulfide polymer, it reduces swelling and strength reduction when the cured product is immersed in warm water. Can be made.
本発明で用いる液状ポリサルファイドポリマーは、好ましくは下記式（２）で示される。
ＨＳ−（Ｒ−Ｓx）n−Ｒ−ＳＨ （２）
（ただし、Ｒは−Ｏ−ＣＨ2−Ｏ−結合を含む２価あるいは３価の有機基、ｎは１〜２００の整数であり、好ましくは１〜５０の整数である。ｘは１〜５の整数でｘの平均値は１〜２．５である。）
The liquid polysulfide polymer used in the present invention is preferably represented by the following formula (2).
HS- (R- Sx ) n- R-SH (2)
(However, R is a divalent or trivalent organic group containing a —O—CH 2 —O— bond, n is an integer of 1 to 200, and preferably an integer of 1 to 50. x is 1 to 5) And the average value of x is 1 to 2.5.)
前記式（２）において、Ｒは、好ましくは、−Ｏ−ＣＨ2−Ｏ−結合と、直鎖アルキレン基または分岐アルキレン基を含む有機基である。Ｒは、より好ましくは−Ｏ−ＣＨ2−Ｏ−結合と分岐アルキレン基を含む有機基であるとよい。直鎖または分岐アルキレン基は、好ましくは、−Ｏ−ＣＨ2−Ｏ−結合のモル数に対して、０〜７０モル％である。 In the formula (2), R is preferably an organic group containing a —O—CH 2 —O— bond and a linear alkylene group or a branched alkylene group. R is more preferably an organic group containing a —O—CH 2 —O— bond and a branched alkylene group. The linear or branched alkylene group is preferably 0 to 70 mol% with respect to the number of moles of the —O—CH 2 —O— bond.
Ｒは、好ましくは、
−Ｃ2Ｈ4−Ｏ−ＣＨ2−Ｏ−Ｃ2Ｈ4−
を５０モル％以上含有する。さらに好ましくは、
−Ｃ2Ｈ4−Ｏ−ＣＨ2−Ｏ−Ｃ2Ｈ4−
を７０モル％以上含有する。
R is preferably
—C 2 H 4 —O—CH 2 —O—C 2 H 4 —
Is contained in an amount of 50 mol% or more. More preferably,
—C 2 H 4 —O—CH 2 —O—C 2 H 4 —
70 mol% or more.
分岐アルキレン基は、好ましくは、トリハロ有機化合物由来の多官能成分で、下記式（３）で示される有機基である。
分岐トリハロ有機化合物として好ましいのは、トリハロアルキル化合物であり、より好ましいのは、トリハロプロパンである。好ましいトリハロプロパンのハロゲン原子は、塩素、臭素、およびヨウ素であり、より好ましいハロゲン原子は塩素原子である。 Preferred as the branched trihalo organic compound is a trihaloalkyl compound, and more preferred is trihalopropane. Preferred halogen atoms of trihalopropane are chlorine, bromine, and iodine, and more preferred halogen atoms are chlorine atoms.
本発明で用いる液状ポリサルファイドポリマーは、前記式（２）のｎが１〜２００の整数、好ましくは１〜５０の整数である。液状ポリサルファイドポリマーは、室温で液状であり、数平均分子量が、好ましくは５００〜５０，０００、より好ましくは、１，０００〜１０，０００である。 In the liquid polysulfide polymer used in the present invention, n in the formula (2) is an integer of 1 to 200, preferably an integer of 1 to 50. The liquid polysulfide polymer is liquid at room temperature, and the number average molecular weight is preferably 500 to 50,000, more preferably 1,000 to 10,000.
さらに、前記式（２）のｘは１〜５の整数、好ましくは１〜３の整数であり、ｘの平均値が１〜２．５である。また、特にｘの平均値が２未満であるときには、低粘度、低ガラス転移温度、高耐熱性の効果がある。 Furthermore, x in the formula (2) is an integer of 1 to 5, preferably an integer of 1 to 3, and the average value of x is 1 to 2.5. In particular, when the average value of x is less than 2, there are effects of low viscosity, low glass transition temperature, and high heat resistance.
本発明で用いる液状ポリサルファイドポリマーは、従来の固体ポリサルファイドの形成を経由する製造方法及び、相間移動触媒を用いた固体ポリサルファイドの形成を含まない特許第４２２７７８７号記載の製造方法等、いずれの方法にも限定されることなく得ることができる。 The liquid polysulfide polymer used in the present invention may be produced by any of the conventional methods such as the production method via formation of solid polysulfide and the production method described in Japanese Patent No. 4227787 which does not include formation of solid polysulfide using a phase transfer catalyst. It can be obtained without limitation.
本発明の硬化型組成物は、二酸化マンガンを液状ポリサルファイドポリマーの硬化剤として用いる際に、作業性及び硬化後の物性を改良する目的で、必要に応じて、可塑剤、充填材、硬化促進剤、接着促進剤、顔料などの添加剤を含有する事ができる。好ましくは充填材、可塑剤、硬化促進剤から選ばれる少なくとも一つを含有するとよい。 When using manganese dioxide as a curing agent for a liquid polysulfide polymer, the curable composition of the present invention is a plasticizer, a filler, a curing accelerator, if necessary, for the purpose of improving workability and physical properties after curing. Further, additives such as adhesion promoters and pigments can be contained. Preferably, at least one selected from fillers, plasticizers, and curing accelerators may be contained.
可塑剤としては、フタル酸ジブチル、フタル酸ブチルベンジル、フタル酸アルキル（Ｃ7−Ｃ9）ベンジルなどのフタル酸エステル、塩素化パラフィン、ジプロピレングリコールジベンゾエート、ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、ジプロピレングリコールモノベンゾエート、水添ターフェニル、特開２００４―５１９１８公報記載の炭化水素系可塑剤、特願２０１１−１６７３３０記載のハロゲン末端硫黄含有重合体などが挙げられる。好ましい可塑剤としては、フタル酸エステル、塩素化パラフィン、ジプロピレングリコールジベンゾエート、ハロゲン末端硫黄含有重合体から選ばれる少なくとも一つであるとよい。 Plasticizers include phthalates such as dibutyl phthalate, butyl benzyl phthalate, alkyl phthalate (C 7 -C 9 ) benzyl, chlorinated paraffin, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate , Dipropylene glycol monobenzoate, hydrogenated terphenyl, hydrocarbon plasticizer described in JP-A-2004-51918, and halogen-terminated sulfur-containing polymer described in Japanese Patent Application No. 2011-167330. A preferable plasticizer is at least one selected from phthalic acid esters, chlorinated paraffins, dipropylene glycol dibenzoates, and halogen-terminated sulfur-containing polymers.
可塑剤の添加量は、硬化物の硬度、強度や伸び、さらには硬化前の硬化型組成物の粘度の設計によって設定されるが、液状ポリサルファイドポリマー１００重量部に対して１〜１００重量部であることが好ましい。可塑剤の添加量が１００重量部を超えると非反応性の液状物が多くなり硬度が保てない場合がある。より好ましくは１〜５０重量部であり、さらにより好ましくは１〜３０重量部である。 The addition amount of the plasticizer is set by the hardness, strength and elongation of the cured product, and further by the design of the viscosity of the curable composition before curing, but it is 1 to 100 parts by weight with respect to 100 parts by weight of the liquid polysulfide polymer. Preferably there is. If the added amount of the plasticizer exceeds 100 parts by weight, the amount of non-reactive liquid may increase and the hardness may not be maintained. More preferably, it is 1-50 weight part, More preferably, it is 1-30 weight part.
充填材としては、例えば炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、シリカ、ケイ酸塩、硫酸塩などの無機充填材やカーボンブラックなどが挙げられる。また、ポリアミドやポリエチレンのような軽量ポリマー充填材、シリカ、アクリロニトリルやメタクリロニトリルや塩化ビニリデンなどの熱可塑性バルーン（熱膨張性マイクロカプセル）、フェノールやエポキシなどの熱硬化性バルーン、シラスやフライアッシュやガラスやアルミナなどの無機系バルーンなどの中空充填材、などが挙げられる。なお、充填材は２種類以上用いてもよく、いずれの充填材も、表面を脂肪酸、樹脂酸、界面活性剤、シランカップリング剤、パラフィンなどで処理したものを使用してもよい。好ましい充填材としては、カーボンブラック、炭酸カルシウム、シリカ、マイクロバルーンから選ばれる少なくとも一つであるとよい。なお、炭酸カルシウムは、重質炭酸カルシウム、コロイド炭酸カルシウムが好ましい。一般に、重質炭酸カルシウムは、石灰石原石を機械的に粉砕・分級して所望の粒度とし得られた炭酸カルシウムである。またコロイド炭酸カルシウムは、石灰石原石をコークス等で混焼し、一旦酸化カルシウム（生石灰）を作製し、それを水と反応させて水酸化カルシウム（消石灰）とし、焼成時に発生した炭酸ガスと反応せしめ、所望の粒径、粒子形状とし得られた炭酸カルシウムである。 Examples of the filler include inorganic fillers such as calcium carbonate, aluminum oxide, aluminum hydroxide, silica, silicate, sulfate, and carbon black. Also, lightweight polymer fillers such as polyamide and polyethylene, thermoplastic balloons (thermally expandable microcapsules) such as silica, acrylonitrile, methacrylonitrile and vinylidene chloride, thermosetting balloons such as phenol and epoxy, shirasu and fly ash And hollow fillers such as inorganic balloons such as glass and alumina. Two or more kinds of fillers may be used, and any of the fillers may have a surface treated with a fatty acid, a resin acid, a surfactant, a silane coupling agent, paraffin, or the like. A preferred filler is at least one selected from carbon black, calcium carbonate, silica, and microballoons. The calcium carbonate is preferably heavy calcium carbonate or colloidal calcium carbonate. Generally, heavy calcium carbonate is calcium carbonate obtained by mechanically crushing and classifying raw limestone to obtain a desired particle size. In addition, colloidal calcium carbonate is obtained by co-firing raw limestone with coke, etc., once producing calcium oxide (quick lime), reacting it with water to form calcium hydroxide (slaked lime), and reacting with carbon dioxide gas generated during firing, Calcium carbonate obtained to have a desired particle size and particle shape.
充填材の添加量は、液状ポリサルファイドポリマー１００重量部に対して０．１〜５００重量部であることが好ましい。充填材の添加量が０．１重量部未満では十分な補強硬化が得られず、５００重量部を超えると硬化型組成物の粘度が高くなり作業性が低下し好ましくない。より好ましくは１〜３００重量部であり、さらにより好ましくは、１０〜２００重量部であり、もっと好ましくは、３０〜６０重量部である。 The amount of filler added is preferably 0.1 to 500 parts by weight with respect to 100 parts by weight of the liquid polysulfide polymer. When the addition amount of the filler is less than 0.1 parts by weight, sufficient reinforcement and curing cannot be obtained, and when it exceeds 500 parts by weight, the viscosity of the curable composition becomes high and workability is lowered, which is not preferable. More preferably, it is 1-300 weight part, More preferably, it is 10-200 weight part, More preferably, it is 30-60 weight part.
硬化促進剤としては、アルデヒド・アンモニア及びアルデヒド・アミン系、チオウレア系、グアニジン系、チアゾール系、スルフェンアミド系、チウラム系、ジチオカルバミン酸塩系、キサントゲン酸塩系などの加硫促進剤が挙げられる。具体的には、トリス（ジメチルアミノメチル）フェノール、ジフェニルグアニジン、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ヘキサメチレンテトラミンなどが挙げられる。好ましい硬化促進剤としては、チウラム系硬化促進剤、グアニジン系硬化促進剤から選ばれる少なくとも一つであるとよい。上記加硫促進剤は２種類以上を用いても良い。 Curing accelerators include vulcanization accelerators such as aldehyde / ammonia and aldehyde / amine, thiourea, guanidine, thiazole, sulfenamide, thiuram, dithiocarbamate and xanthate. . Specific examples include tris (dimethylaminomethyl) phenol, diphenylguanidine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, hexamethylenetetramine and the like. A preferable curing accelerator is at least one selected from a thiuram curing accelerator and a guanidine curing accelerator. Two or more kinds of the vulcanization accelerators may be used.
硬化促進剤の添加量は、硬化型組成物の硬化速度や、さらには使用温度によって設定されるが、液状ポリサルファイドポリマー１００重量部に対して１〜１０重量部であることが好ましい。硬化促進剤の添加量が１０重量部を超えると反応に関与しなかった残存の促進剤が硬化物の性能を落とす場合がある。より好ましくは１〜５重量部であり、さらにより好ましくは、１〜３重量部である。 Although the addition amount of a hardening accelerator is set with the hardening rate of a curable composition, and also use temperature, it is preferable that it is 1-10 weight part with respect to 100 weight part of liquid polysulfide polymers. When the addition amount of the curing accelerator exceeds 10 parts by weight, the remaining accelerator that is not involved in the reaction may deteriorate the performance of the cured product. More preferably, it is 1-5 weight part, More preferably, it is 1-3 weight part.
接着促進剤としては加水分解性シリル基と反応性有機官能基とを含有するシランカップリング剤が挙げられる。具体的には、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィドなどが挙げられる。また、特開平６−２７１８３３号公報に記載のポリサルファイドポリマー“チオコールＬＰ−３”と３―グリドキシプロピルトリメトキシシランを反応させて合成した末端トリメトキシシラン変性ポリサルファイドポリマーもシランカップリング剤として用いることができる。これらシランカップリング剤は２種以上を用いてもよい。 Examples of the adhesion promoter include a silane coupling agent containing a hydrolyzable silyl group and a reactive organic functional group. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Triethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (amino Ethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- Examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and bis (triethoxysilylpropyl) tetrasulfide. Further, a terminal trimethoxysilane-modified polysulfide polymer synthesized by reacting polysulfide polymer “thiocol LP-3” and 3-gridoxypropyltrimethoxysilane described in JP-A-6-271833 is also used as a silane coupling agent. Can do. Two or more of these silane coupling agents may be used.
本発明の硬化型組成物で得られる硬化物は、耐油性、耐候性、水密性、気密性に優れた特徴を持ち、さらに温水浸漬時の体積膨潤が極めて小さい特徴を持つ。これらの特徴は、シーリング材、接着剤および塗料などに好適である。特に、温水浸漬時の膨潤が極めて小さい特徴は、サッシに溜まった水への耐久性を求められる複層ガラス用シーリング材に最適である。世界の市場で最大のシェアを持つ、二酸化マンガンを硬化剤とする従来のポリサルファイド系複層ガラスシーリング材は、８０℃温水浸漬１０日間で２０％以上の膨潤がある。したがって、ポリサルファイド系シーリング材において耐久性を向上させるためには、８０℃温水浸漬１０日後の体積膨潤率を２０％未満に押さえることが好ましい。より好ましくは、８０℃温水浸漬１０日後の体積膨潤率が１０％未満である。 The cured product obtained by the curable composition of the present invention has excellent oil resistance, weather resistance, water tightness, and air tightness, and also has extremely small volume swelling when immersed in warm water. These characteristics are suitable for sealing materials, adhesives, paints and the like. In particular, the feature of extremely small swelling when immersed in warm water is most suitable for a sealing material for double-glazed glass that requires durability to water accumulated in a sash. The conventional polysulfide-based multi-layer glass sealing material using manganese dioxide as a curing agent, which has the largest market share in the world market, has a swelling of 20% or more in 10 days of hot water immersion at 80 ° C. Therefore, in order to improve durability in the polysulfide-based sealing material, it is preferable to keep the volume swelling rate after 10 days of 80 ° C. hot water immersion to less than 20%. More preferably, the volume swelling rate after 10 days of 80 ° C. hot water immersion is less than 10%.
体積膨潤率の測定は様々な方法があるが、空気中の重量と水中の重量から体積を求め、温水浸漬前後で体積の変化率（％）を求める方法が簡易かつ精度が良い。サンプルの形状はより浸漬の影響を受けやすいように、厚みを薄く調整する必要があるが、データの再現性より、２ｍｍ厚以下のシートとし、３０×３０ｍｍ以上の面積とするのが好ましい。 There are various methods for measuring the volume swelling rate, but the method of obtaining the volume from the weight in air and the weight in water and obtaining the volume change rate (%) before and after immersion in warm water is simple and accurate. The thickness of the sample needs to be adjusted to be thin so that it is more susceptible to immersion. However, from the reproducibility of the data, it is preferable to use a sheet having a thickness of 2 mm or less and an area of 30 × 30 mm or more.
本発明を以下の実施例によりさらに詳細に説明する。以下に記載の「部」は特に断りのない限り重量基準の「重量部」である。 The invention is illustrated in more detail by the following examples. The “parts” described below are “parts by weight” based on weight unless otherwise specified.
二酸化マンガンの結晶構造の同定と層間距離の算出には、粉末Ｘ線回折測定（スペクトリス株式会社製Ｘ’Ｐｅｒｔ ＰＲＯ ＭＲＤ）を行い、Ｘ線回折チャートを得た。標準回折チャートとのピーク比較により結晶構造の同定を行い、００１反射に指数付けされるピークの面間隔がバーネサイト構造の層間距離に相当するとして層間距離を算出した。 For identification of the crystal structure of manganese dioxide and calculation of the interlayer distance, powder X-ray diffraction measurement (X'Pert PRO MRD manufactured by Spectris Co., Ltd.) was performed to obtain an X-ray diffraction chart. The crystal structure was identified by comparing the peak with the standard diffraction chart, and the interlayer distance was calculated assuming that the interplanar spacing of the peak indexed to the 001 reflection corresponds to the interlayer distance of the burntite structure.
化学組成比の算出には、Ｎａに関しては原子吸光法、Ｍｎに関しては酸化還元滴定法、その他の金属に関してはＩＣＰ発光分光分析法（ＩＣＰ−ＡＥＳ法）を用いて定量を行った。なお、表１に記載した化学分析結果は、二酸化マンガン中の各金属の含量（重量％）を表わした。 For calculation of the chemical composition ratio, quantification was performed using atomic absorption method for Na, oxidation-reduction titration method for Mn, and ICP emission spectroscopic analysis method (ICP-AES method) for other metals. In addition, the chemical analysis result described in Table 1 represents the content (% by weight) of each metal in manganese dioxide.
合成例１
塩化マンガンニ水和物１８８．７部を蒸留水３０００部に加えて溶解した水溶液（Ａ）と、苛性ソーダ８２５部と過酸化水素２１６．２部と蒸留水３７５０部からなる水溶液（Ｂ）を準備した。水溶液（Ａ）、（Ｂ）いずれも、１０℃以下に保持した後、回転数８００ｒｐｍで攪拌しながら、水溶液（Ｂ）を水溶液（Ａ）に１２０分間かけて加えた。添加完了後、更に５時間攪拌を行った。その後、懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗し、ろ物（１）を得た。ろ物（１）を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、合成例１の粉末試料を得た。
Synthesis example 1
An aqueous solution (A) prepared by adding 188.7 parts of manganese chloride dihydrate to 3000 parts of distilled water and an aqueous solution (B) comprising 825 parts of caustic soda, 216.2 parts of hydrogen peroxide, and 3750 parts of distilled water were prepared. . Both aqueous solutions (A) and (B) were kept at 10 ° C. or lower, and then the aqueous solution (B) was added to the aqueous solution (A) over 120 minutes while stirring at a rotation speed of 800 rpm. After the addition was completed, the mixture was further stirred for 5 hours. Thereafter, the suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm) to obtain a filtrate (1). Filtrate (1) was collected, dried at 80 ° C. for 10.5 hours, and then crushed in a mortar to obtain a powder sample of Synthesis Example 1.
得られた粉末試料のＸ線回折チャートを図１（ａ）に示す。また、比較のため、単斜晶系ナトリウムバーネサイトＮａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏの標準Ｘ線回折チャートを図１（ｂ）に、斜方晶系ナトリウムバーネサイトＮａ4Ｍｎ14Ｏ27・９Ｈ2Ｏの標準Ｘ線回折チャートを図１（ｃ）に示す。図１（ａ）には約１２．４°と約２５．０°に明瞭なピークがみられ、それらは図１（ｂ）に示す単斜晶系ナトリウムバーネサイトＮａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏのピークに一致することから、それぞれは面間隔７．１３オングストロームの００１反射と３．５６オングストロームの００２反射に指数付けされる。 An X-ray diffraction chart of the obtained powder sample is shown in FIG. For comparison, a standard X-ray diffraction chart of the sodium monoclinic bar Ne site Na 0.55 Mn 2 O 4 · 1.5H 2 O in FIG. 1 (b), orthorhombic sodium bar Ne site Na 4 A standard X-ray diffraction chart of Mn 14 O 27 · 9H 2 O is shown in FIG. In FIG. 1A, clear peaks are observed at about 12.4 ° and about 25.0 °, which are monoclinic sodium banesite Na 0.55 Mn 2 O 4. Since they coincide with the 1.5 H 2 O peak, each is indexed to a 001 reflection with a spacing of 7.13 Å and a 002 reflection with 3.56 Å.
それに対して、図１（ｃ）の斜方晶系ナトリウムバーネサイトＮａ4Ｍｎ14Ｏ27・９Ｈ2ＯのＸ線回折チャートでは、図１（ａ）で確認されない約１５．８°の１２０反射に指数付けされるピークがみられ、また、約１２．４°と約２５．０°のピーク強度比が図１（ａ）とは異なる。これらの結果より、図１（ａ）の合成例１の試料は、斜方晶系ではなく、単斜晶系のバーネサイト構造を有している。また、単斜晶系のバーネサイト構造においては、００１反射に指数付けされる約１２．４°のピークの面間隔が層間距離に該当することから、その層間距離は７．１３オングストロームであることがわかる。また、合成例１の化学組成比を表１に示す。 On the other hand, the X-ray diffraction chart of orthorhombic sodium banesite Na 4 Mn 14 O 27 · 9H 2 O in FIG. 1 (c) shows a 120 ° of about 15.8 ° which is not confirmed in FIG. Peaks indexed by reflection are observed, and the peak intensity ratio of about 12.4 ° and about 25.0 ° is different from that in FIG. From these results, the sample of Synthesis Example 1 in FIG. 1A has a monoclinic birnessite structure, not an orthorhombic system. Further, in the monoclinic birnessite structure, the surface distance of the peak of about 12.4 ° indexed to the 001 reflection corresponds to the interlayer distance, and therefore the interlayer distance may be 7.13 angstroms. Recognize. The chemical composition ratio of Synthesis Example 1 is shown in Table 1.
これらの結果から、合成例１はナトリウム含量２．９３重量％の単斜晶系のナトリウムバーネサイトＮａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏ単層である。 From these results, Synthesis Example 1 is a monoclinic sodium birnessite Na 0.55 Mn 2 O 4 .1.5H 2 O single layer with a sodium content of 2.93 wt%.
合成例２
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化カルシウム二水和物４４１部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し合成例２の試料を得た。
Synthesis example 2
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 441 parts of calcium chloride dihydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Then, the sample of the synthesis example 2 was obtained by crushing with a mortar.
得られた合成例２の試料のＸ線回折チャートを図２（ａ）に示す。また、比較のため、単斜晶系ナトリウムバーネサイトＮａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏの標準Ｘ線回折チャートを図２（ｂ）に、斜方晶系ナトリウムバーネサイトＮａ4Ｍｎ14Ｏ27・９Ｈ2Ｏの標準Ｘ線回折チャートを図２（ｃ）に示す。図２（ａ）を上述した図１（ａ）と同様に解析することより、合成例２で得られた試料が単斜晶系のバーネサイト構造を有し層間距離が７．０１オングストロームであることがわかる。また、化学組成比を表１に示す。これらの結果から、合成例２はナトリウム含量０．０１重量％の、層間にカルシウムイオンが導入された単斜晶系バーネサイトである。 The X-ray diffraction chart of the obtained sample of Synthesis Example 2 is shown in FIG. For comparison, a standard X-ray diffraction chart of the sodium monoclinic bar Ne site Na 0.55 Mn 2 O 4 · 1.5H 2 O in FIG. 2 (b), orthorhombic sodium bar Ne site Na 4 A standard X-ray diffraction chart of Mn 14 O 27 · 9H 2 O is shown in FIG. By analyzing FIG. 2A in the same manner as FIG. 1A described above, the sample obtained in Synthesis Example 2 has a monoclinic birnessite structure and the interlayer distance is 7.01 angstroms. I understand. The chemical composition ratio is shown in Table 1. From these results, Synthesis Example 2 is a monoclinic birnessite having a sodium content of 0.01% by weight and having calcium ions introduced between layers.
合成例３
合成例１と同様にして得たろ物（１）４００部を、予め用意した酢酸３７０部と蒸留水１４７００部からなる水溶液に加え、１２時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で２．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例３はナトリウム含量０．０７重量％の、層間にプロトンが導入された単斜晶系バーネサイトである。
Synthesis example 3
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to an aqueous solution composed of 370 parts of acetic acid and 14700 parts of distilled water, and stirred for 12 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 2.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 3 is a monoclinic birnessite having a sodium content of 0.07% by weight and having protons introduced between layers.
合成例４
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化アンモニウム６７５．７部と蒸留水３０００部からなる水溶液に加え、１２時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、３０℃で３０時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例４はナトリウム含量０．０７重量％の、層間にアンモニウムイオンが導入された単斜晶系バーネサイトである。
Synthesis example 4
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to an aqueous solution prepared by 675.7 parts of ammonium chloride and 3000 parts of distilled water and stirred for 12 hours. Next, the obtained suspension is filtered and washed with water until the electric conductivity of the filtrate reaches 100 microsiemens (μS / cm), and then the filtrate is collected and dried at 30 ° C. for 30 hours. The sample was obtained by crushing in a mortar. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 4 is a monoclinic birnessite having a sodium content of 0.07% by weight and having ammonium ions introduced between layers.
合成例５
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化カルシウム二水和物１３２部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例５はナトリウム含量０．０９重量％の、層間にカルシウムイオンが導入された単斜晶系バーネサイトである。
Synthesis example 5
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 132 parts of calcium chloride dihydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 5 is a monoclinic birnessite having a sodium content of 0.09% by weight and having calcium ions introduced between layers.
合成例６
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化カルシウム二水和物１３２部と蒸留水３０００部からなる水溶液に加え、９時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例６はナトリウム含量０．１６重量％の、層間にカルシウムイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 6
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 132 parts of calcium chloride dihydrate and 3000 parts of distilled water and stirred for 9 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 6 is a monoclinic birnessite having a sodium content of 0.16% by weight and calcium ions introduced between layers.
合成例７
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化カルシウム二水和物６６部と蒸留水３０００部からなる水溶液に加え、１０時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例７はナトリウム含量０．３０重量％の、層間にカルシウムイオンが導入された単斜晶系バーネサイトである。
Synthesis example 7
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 66 parts of calcium chloride dihydrate and 3000 parts of distilled water and stirred for 10 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 7 is a monoclinic birnessite having a sodium content of 0.30% by weight and having calcium ions introduced between layers.
合成例８
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化カルシウム二水和物６６部と蒸留水３０００部からなる水溶液に加え、４．５時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例８はナトリウム含量０．５９重量％の、層間にカルシウムイオンが導入された単斜晶系バーネサイトである。
Synthesis example 8
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 66 parts of calcium chloride dihydrate and 3000 parts of distilled water and stirred for 4.5 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 8 is a monoclinic birnessite having a sodium content of 0.59% by weight and having calcium ions introduced between layers.
合成例９
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化マグネシウム六水和物６０９．９部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、１００℃で６０時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例９はナトリウム含量０．０１重量％の、層間にマグネシウムイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 9
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 609.9 parts of magnesium chloride hexahydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension is filtered, washed with water until the conductivity of the filtrate reaches 100 microsiemens (μS / cm), and then the filtrate is collected and dried at 100 ° C. for 60 hours. The sample was obtained by crushing in a mortar. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 9 is a monoclinic birnessite having a sodium content of 0.01% by weight and having magnesium ions introduced between layers.
合成例１０
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化鉄(III)二水和物８１１．１部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１０はナトリウム含量０．００重量％の、層間に鉄(III)イオンが導入された単斜晶系バーネサイトである。
Synthesis Example 10
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 811.1 parts of iron (III) chloride dihydrate and 3000 parts of distilled water, and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 10 is a monoclinic birnessite having a sodium content of 0.00% by weight and having iron (III) ions introduced between layers.
合成例１１
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化ランタン二水和物１１１４．１部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１１はナトリウム含量０．０１重量％の、層間にランタンイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 11
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution of 1114.1 parts of lanthanum chloride dihydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 11 is monoclinic birnessite having a sodium content of 0.01% by weight and having lanthanum ions introduced between layers.
合成例１２
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化亜鉛４０８．９部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１２はナトリウム含量０．０７重量％の、層間に亜鉛イオンが導入された単斜晶系バーネサイトである。
Synthesis Example 12
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 408.9 parts of zinc chloride and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 12 is a monoclinic birnessite having a sodium content of 0.07% by weight and zinc ions introduced between layers.
合成例１３
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化バリウムニ水和物７３２．８部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１３はナトリウム含量０．０２重量％の、層間にバリウムイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 13
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 732.8 parts of barium chloride dihydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 13 is a monoclinic birnessite having a sodium content of 0.02% by weight and having barium ions introduced between layers.
合成例１４
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化ストロンチウム六水和物７９９．９部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、８０℃で１０．５時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１４はナトリウム含量０．０１重量％の、層間にストロンチウムイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 14
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 799.9 parts of strontium chloride hexahydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension was filtered and washed with water until the electric conductivity of the filtrate reached 100 microsiemens (μS / cm), and then the filtrate was collected and dried at 80 ° C. for 10.5 hours. Thereafter, the sample was crushed in a mortar to obtain a sample. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 14 is a monoclinic birnessite having a sodium content of 0.01% by weight and having strontium ions introduced between layers.
合成例１５
合成例１と同様にして得たろ物（１）４００部を、予め用意した塩化ニッケル二水和物７１３．１部と蒸留水３０００部からなる水溶液に加え、２４時間攪拌した。次に、得られた懸濁液の濾過を行い、ろ液の電導度が１００マイクロシーメンス（μＳ／ｃｍ）となるまで水洗した後、ろ物を回収し、１００℃で６８時間乾燥した後、乳鉢で解砕し、試料を得た。この試料を合成１と同様に評価し、その層間距離と化学組成比を表１に示す。これらの結果から、合成例１５はナトリウム含量０．０１重量％の、層間にニッケルイオンが導入された単斜晶系バーネサイトである。
Synthesis Example 15
400 parts of the filtrate (1) obtained in the same manner as in Synthesis Example 1 was added to a previously prepared aqueous solution consisting of 713.1 parts of nickel chloride dihydrate and 3000 parts of distilled water and stirred for 24 hours. Next, the obtained suspension is filtered and washed with water until the electric conductivity of the filtrate reaches 100 microsiemens (μS / cm), and then the filtrate is collected and dried at 100 ° C. for 68 hours. The sample was obtained by crushing in a mortar. This sample was evaluated in the same manner as in Synthesis 1, and the interlayer distance and chemical composition ratio are shown in Table 1. From these results, Synthesis Example 15 is a monoclinic birnessite having a sodium content of 0.01% by weight and having nickel ions introduced between layers.
表１に、合成例１〜１５の各サンプルの層間距離、各金属の含量を示した。なお、合成例１〜１５のサンプルはいずれも、層間距離が約７オングスロトームであり単斜晶系のバーネサイト単層構造を有する二酸化マンガンであることを確認した。また合成例２〜５、９〜１５の各サンプルは、層間のナトリウム含量が０．１５重量％以下である。 Table 1 shows the interlayer distance of each sample of Synthesis Examples 1 to 15 and the content of each metal. In addition, it was confirmed that all samples of Synthesis Examples 1 to 15 were manganese dioxide having a monoclinic birnessite single layer structure with an interlayer distance of about 7 angstrom. In addition, each sample of Synthesis Examples 2 to 5 and 9 to 15 has a sodium content between layers of 0.15% by weight or less.
また市販品１として二酸化マンガン（Ｈｏｎｅｙｗｅｌｌ社製ＴｙｐｅＦＡ）の結晶構造、層間距離、化学組成比を合成例１と同様にして評価した結果、市販品１の結晶構造は単斜晶系のバーネサイト単層構造であることを確認し、その化学組成比を表１に示した。 Moreover, as a result of evaluating the crystal structure, interlayer distance, and chemical composition ratio of manganese dioxide (TypeFA manufactured by Honeywell) as the commercial product 1 in the same manner as in Synthesis Example 1, the crystal structure of the commercial product 1 is a monoclinic birnessite monolayer. The structure was confirmed, and the chemical composition ratio is shown in Table 1.
さらに市販品２として、アルカリ処理はされているが、層構造を持たない斜方晶系ラムスデライト構造を有する二酸化マンガン（東ソー社製ＦＭＨ）を準備した。市販品２の二酸化マンガンの結晶構造は斜方晶系ラムスデライト構造であり、その技術資料に記載された化学組成比を表１に示した。 Furthermore, as a commercial product 2, manganese dioxide (FMSO manufactured by Tosoh Corporation) having an orthorhombic ramsdellite structure that was alkali-treated but did not have a layer structure was prepared. The crystal structure of manganese dioxide in the commercial product 2 is an orthorhombic ramsdellite structure, and the chemical composition ratio described in the technical data is shown in Table 1.
実施例１
下記の配合に基づき、主剤として、液状ポリサルファイドポリマー（チオコール「ＬＰ−２３」、東レ・ファインケミカル社製）、フタル酸ブチルベンジル、沈降炭酸カルシウム、重質炭酸カルシウム、３−グリシドキシプロピルトリメトキシシランをミキサー用いて混合した。また、硬化剤として、合成例２の二酸化マンガン、フタル酸ブチルベンジル、フタル酸系可塑剤、テトラメチルチウラムジスルフィド、重質炭酸カルシウム、ＳＦＲカーボンを、三本ロールミルを用いて混練した。
Example 1
Based on the following formulation, as a main agent, liquid polysulfide polymer (thiocol "LP-23", manufactured by Toray Fine Chemical Co., Ltd.), butyl benzyl phthalate, precipitated calcium carbonate, heavy calcium carbonate, 3-glycidoxypropyltrimethoxysilane Were mixed using a mixer. Further, the manganese dioxide, butylbenzyl phthalate, phthalate plasticizer, tetramethylthiuram disulfide, heavy calcium carbonate, and SFR carbon of Synthesis Example 2 were kneaded as a curing agent using a three-roll mill.
主剤の組成
・チオコール「ＬＰ−２３」（東レ・ファインケミカル社製） １００重量部
・フタル酸ブチルベンジル（大八化学社製） ３７重量部
・沈降炭酸カルシウム（白石カルシウム社製白艶華ＣＣ） ６５重量部
・重質炭酸カルシウム（白石カルシウム社製ホワイトンＳＳＢ赤） ９０重量部
・３−グリシドキシプロピルトリメトキシシラン
（東レ・ダウコーニング社製ＳＨ−６０４０） ３重量部
Composition of base agent: Thiocol "LP-23" (Toray Fine Chemical Co., Ltd.) 100 parts by weight, butylbenzyl phthalate (Daihachi Chemical Co., Ltd.) 37 parts by weight, precipitated calcium carbonate (Shiraishi Calcium Co., Ltd., White Glossy CC) 65 parts by weight・ Heavy calcium carbonate (White SSB Red, manufactured by Shiraishi Calcium Co., Ltd.) 90 parts by weight ・ 3-Glycidoxypropyltrimethoxysilane (Toray, Dow Corning SH-6040) 3 parts by weight
硬化剤の組成
・二酸化マンガン（合成例２） １０重量部
・フタル酸ブチルベンジル（大八化学社製） ２．５重量部
・フタル酸系可塑剤（フェロ社製サンチサイザー２７８） １０．５重量部
・テトラメチルチウラムジスルフィド
（大内新興化学工業社製ノクセラーＴＴ） ０．５重量部
・重質炭酸カルシウム（日東粉化工業社製ＮＣＣ＃４１０） ５重量部
・ＳＲＦカーボン ０．５重量部
上記により得られた主剤と硬化剤を手練りでよく混練して、その混合物からなる硬化型組成物を得た。
Composition of curing agent: Manganese dioxide (Synthesis example 2) 10 parts by weight-Butyl benzyl phthalate (Daihachi Chemical Co., Ltd.) 2.5 parts by weight-Phthalic acid plasticizer (Santisizer 278, Ferro Corporation) 10.5 weight Parts ・ Tetramethylthiuram disulfide (Nouchira TT manufactured by Ouchi Shinsei Chemical Co., Ltd.) 0.5 parts by weight ・ Heavy calcium carbonate (NCC # 410 manufactured by Nitto Flour Chemical Co., Ltd.) 5 parts by weight ・ SRF carbon 0.5 parts by weight The main agent and the curing agent obtained by the above were kneaded well by hand to obtain a curable composition comprising the mixture.
得られた硬化型組成物を、２ｍｍの隙間ができるように調整した鉄板で挟み込み、２３℃５０％ＲＨ雰囲気下で７日間養生した。得られたシートから３枚の３０ｍｍ×３０ｍｍの試験片に切断した。各試験片を８０℃の温水に１０日間浸漬した後、体積膨潤率を下記の式により求めた。３枚の試験片の平均値を体積膨潤率として表２に示す。
体積膨潤率（％）＝[（ｗ３−ｗ４）−（ｗ１−ｗ２）]／（ｗ１−ｗ２）×１００
（式中、ｗ１は空気中での初期重量、ｗ２は水中での初期重量、ｗ３は空気中での浸漬後重量、ｗ４は水中での浸漬後重量である。）
The obtained curable composition was sandwiched between iron plates adjusted to have a gap of 2 mm and cured for 7 days in an atmosphere of 23 ° C. and 50% RH. The obtained sheet was cut into three 30 mm × 30 mm test pieces. Each test piece was immersed in warm water at 80 ° C. for 10 days, and then the volume swelling ratio was determined by the following formula. Table 2 shows the average value of the three test pieces as the volume swelling ratio.
Volume swelling ratio (%) = [(w3-w4)-(w1-w2)] / (w1-w2) × 100
(W1 is the initial weight in air, w2 is the initial weight in water, w3 is the weight after immersion in air, and w4 is the weight after immersion in water.)
実施例２、３
硬化剤として、実施例１の合成例２の二酸化マンガンの代わりに、合成例３、４の二酸化マンガンを用いて、実施例１と同様にして試験片を作成し、体積膨潤率を求めた。その結果を表２に示す。
Examples 2 and 3
A test piece was prepared in the same manner as in Example 1 using the manganese dioxide of Synthesis Examples 3 and 4 instead of the manganese dioxide of Synthesis Example 2 of Example 1 as a curing agent, and the volume swelling ratio was determined. The results are shown in Table 2.
比較例１
硬化剤として、実施例１の合成例２の二酸化マンガンの代わりに、合成例１の二酸化マンガンを用いて、実施例１と同様にして試験片を作成し、体積膨潤率を求めた。結果を表２に示す。
Comparative Example 1
A test piece was prepared in the same manner as in Example 1 using the manganese dioxide of Synthesis Example 1 instead of the manganese dioxide of Synthesis Example 2 of Example 1, and the volume swelling ratio was determined. The results are shown in Table 2.
比較例２
硬化剤として、実施例１の合成例２の二酸化マンガンの代わりに、市販品１（Ｈｏｎｅｙｗｅｌｌ社製ＴｙｐｅＦＡ）の二酸化マンガンを用いて、実施例１と同様にして試験片を作成し、体積膨潤率を求めた。結果を表２に示す。
Comparative Example 2
A test piece was prepared in the same manner as in Example 1 using manganese dioxide of commercially available product 1 (TypeFA manufactured by Honeywell) instead of manganese dioxide of Synthesis Example 2 of Example 1 as a curing agent, and the volume swelling ratio Asked. The results are shown in Table 2.
表２から、単斜晶系のナトリウムバーネサイト構造を有する二酸化マンガンを使用した硬化型組成物の硬化物の体積膨潤率は、ナトリウム含量２．９３重量％の合成例１において４１％（比較例１）、ナトリウム含量２．７０重量％の市販品において３２％（比較例２）であった。一方で、ナトリウムイオンをカチオン置換した単斜晶系バーネサイト構造を有する二酸化マンガンを含む硬化型組成物は、その硬化物の体積膨潤率が大幅に抑制されることが確認された（実施例１〜３）。 From Table 2, the volume swell ratio of the cured product of the curable composition using manganese dioxide having a monoclinic sodium birnessite structure was 41% in Synthesis Example 1 having a sodium content of 2.93 wt% (comparison) Example 1) and 32% (comparative example 2) in a commercial product with a sodium content of 2.70% by weight. On the other hand, it was confirmed that the curable composition containing manganese dioxide having a monoclinic birnessite structure in which sodium ions were cation-substituted significantly suppressed the volume swelling rate of the cured product (Examples 1 to 3). 3).
実施例４〜７
硬化剤として、単斜晶系のバーネサイト構造中のナトリウム含量の異なる合成例５〜８のカルシウムイオン置換した二酸化マンガンを用いて、実施例１と同様にして試験片を作成し、硬化物の体積膨潤率を求めた。実施例１、比較例１を含めた結果を、ナトリウム含量と共に表３に併記する。
Examples 4-7
A test piece was prepared in the same manner as in Example 1 by using the calcium ion-substituted manganese dioxide of Synthesis Examples 5 to 8 having different sodium contents in the monoclinic birnessite structure as a curing agent, and the volume of the cured product was obtained. The swelling rate was determined. The results including Example 1 and Comparative Example 1 are also shown in Table 3 together with the sodium content.
表３から、ナトリウム含量が少ないほど硬化物の体積膨潤が抑制されており、ナトリウム含量を０．１５重量％以下にした単斜晶系バーネサイト構造を有する二酸化マンガンを使用すると、硬化物の体積膨潤率が１０％未満に低下した。 From Table 3, the volume swelling of the cured product is suppressed as the sodium content is small. When manganese dioxide having a monoclinic birnessite structure with a sodium content of 0.15% by weight or less is used, the volume swelling of the cured product is The rate dropped to less than 10%.
実施例８〜１２
硬化剤として、合成例９〜１３の二酸化マンガン、フタル酸ブチルベンジル、テトラブチルチウラムジスルフィドを、下記の配合に基づき秤量し、三本ロールミルを用いて混練した。ここで各成分の配合量は、実施例１の主剤における液状ポリサルファイドポリマー（チオコール「ＬＰ−２３」、東レ・ファインケミカル社製）１００重量部に対する重量部で表わした。
・二酸化マンガン（合成例９〜１３） １０重量部
・フタル酸ブチルベンジル（大八化学製） １３．０重量部
・テトラブチルチウラムジスルフィド
（大内新興化学工業製 ノクセラーＴＢＴ−Ｎ） ０．５重量部
Examples 8-12
As a curing agent, manganese dioxide, butylbenzyl phthalate, and tetrabutylthiuram disulfide of Synthesis Examples 9 to 13 were weighed based on the following formulation and kneaded using a three-roll mill. Here, the blending amount of each component was expressed in parts by weight with respect to 100 parts by weight of the liquid polysulfide polymer (thiocol “LP-23”, manufactured by Toray Fine Chemical Co., Ltd.) in the main agent of Example 1.
Manganese dioxide (Synthesis Examples 9 to 13) 10 parts by weightButylbenzyl phthalate (Daihachi Chemical) 13.0 parts by weight Tetrabutylthiuram disulfide (Ouchi Shinsei Chemical Industry Noxeller TBT-N) 0.5 weight Part
実施例１で調製した主剤と上記硬化剤を手練りでよく混練して、その混合物からなる硬化型組成物を得た。得られた硬化型組成物を、２ｍｍ厚にして７０℃で１８時間養生した。得られたシートから３枚の３０ｍｍ×３０ｍｍの試験片を切断し、試験片を８０℃の温水に１０日間浸漬した後、実施例１と同様にして、硬化物の体積膨潤率を求めた。３枚の試験片の平均値を体積膨潤率として表４に示す。 The main agent prepared in Example 1 and the above curing agent were well kneaded by hand to obtain a curable composition comprising the mixture. The obtained curable composition was 2 mm thick and cured at 70 ° C. for 18 hours. Three test pieces of 30 mm × 30 mm were cut from the obtained sheet, and the test pieces were immersed in hot water at 80 ° C. for 10 days, and then the volume swelling ratio of the cured product was determined in the same manner as in Example 1. Table 4 shows an average value of the three test pieces as a volume swelling ratio.
実施例１３、１４
硬化剤として、合成例１４，１５の二酸化マンガンを用いて、実施例１と同様にして試験片を作成し、７０℃で７２時間養生した硬化型組成物の体積膨潤率を求めた。その結果を表４に示す。
Examples 13 and 14
Using manganese dioxide of Synthesis Examples 14 and 15 as a curing agent, a test piece was prepared in the same manner as in Example 1, and the volume swelling ratio of the curable composition cured at 70 ° C. for 72 hours was determined. The results are shown in Table 4.
表４より、ナトリウムイオンをカチオン置換して、ナトリウム含量が０．１５重量％以下になるようにした単斜晶系バーネサイト構造を有する二酸化マンガン（実施例８〜１４）は、いずれも硬化物の体積膨潤率が１０％未満であり、実施例１〜３の場合と同様に、耐熱水性が良好である硬化型組成物が得られた。 From Table 4, manganese dioxide (Examples 8 to 14) having a monoclinic birnessite structure in which sodium ions are cation-substituted to have a sodium content of 0.15% by weight or less are all cured products. A curable composition having a volume swelling ratio of less than 10% and good hot water resistance was obtained as in Examples 1-3.
表１〜４の結果より、ナトリウムイオンをカチオン置換して得られる単斜晶系バーネサイト構造を有する二酸化マンガンを含む硬化型組成物は、その硬化物の体積膨潤率が大幅に抑制されることが確認された。さらにナトリウム含量が０．１５重量％以下のとき、硬化物の８０℃温水浸漬後の体積膨潤率を１０％未満にできることが確認された。 From the results of Tables 1 to 4, the curable composition containing manganese dioxide having a monoclinic birnessite structure obtained by cation substitution of sodium ions, the volume swelling rate of the cured product is significantly suppressed. confirmed. Furthermore, when the sodium content was 0.15% by weight or less, it was confirmed that the volume swelling ratio of the cured product after immersion in warm water at 80 ° C. could be less than 10%.
比較例３
硬化剤として、実施例１の合成例２の二酸化マンガンの代わりに、市販品２の二酸化マンガンを用いて、実施例１と同様にして、硬化型組成物を調製し、２ｍｍの隙間ができるように調整した鉄板で挟み込み、２３℃５０％ＲＨ雰囲気下で７日間養生した。しかし、比較例３の硬化型組成物は、硬化しなかった。そこで、さらに続けて７０℃で７２時間養生をしたが、硬化しなかった。
Comparative Example 3
As a curing agent, a curable composition was prepared in the same manner as in Example 1 using the commercially available manganese dioxide in place of the manganese dioxide of Synthesis Example 2 of Example 1 so that a gap of 2 mm was formed. And was cured for 7 days in an atmosphere of 23 ° C. and 50% RH. However, the curable composition of Comparative Example 3 did not cure. Therefore, the film was further cured at 70 ° C. for 72 hours, but did not cure.
Claims (11)
Ｎａ0.55Ｍｎ2Ｏ4・１．５Ｈ2Ｏ （１）
で示される単斜晶系ナトリウムバーネサイトの層間に存在するナトリウムイオンを、一価〜三価のカチオンで置換した単斜晶系カチオン置換バーネサイト型二酸化マンガンからなることを特徴とする二酸化マンガン。 Manganese dioxide used as a curing agent for liquid polysulfide polymer, represented by the following formula (1)
Na 0.55 Mn 2 O 4 .1.5H 2 O (1)
A monoclinic cation-substituted birnessite-type manganese dioxide obtained by substituting sodium ions present between monoclinic sodium birnessite represented by the formula with monovalent to trivalent cations.
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| WO2013129831A1 (en) * | 2012-02-27 | 2013-09-06 | Sk Innovation Co.,Ltd. | Turbostratic na birnessite and method for preparing the same |
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| JPS6322857A (en) * | 1986-05-23 | 1988-01-30 | クツクソン・グル−プ・ピ−エルシ− | Curing composition, production of sodium birnessite and curing of polysulfide polymer |
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