JPH04310584A - Zro2-sio2-cao-based coating composition - Google Patents
Zro2-sio2-cao-based coating compositionInfo
- Publication number
- JPH04310584A JPH04310584A JP7516891A JP7516891A JPH04310584A JP H04310584 A JPH04310584 A JP H04310584A JP 7516891 A JP7516891 A JP 7516891A JP 7516891 A JP7516891 A JP 7516891A JP H04310584 A JPH04310584 A JP H04310584A
- Authority
- JP
- Japan
- Prior art keywords
- sio2
- zro2
- cao
- coating composition
- calcium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title abstract description 36
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 amine compound Chemical class 0.000 claims abstract description 16
- 229940043430 calcium compound Drugs 0.000 claims abstract description 14
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910001622 calcium bromide Inorganic materials 0.000 claims abstract description 5
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims abstract description 5
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000001110 calcium chloride Substances 0.000 claims abstract description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 3
- 229940046413 calcium iodide Drugs 0.000 claims abstract description 3
- 229910001640 calcium iodide Inorganic materials 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000011248 coating agent Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000010408 film Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- GEIYKBJNMPEXRM-UHFFFAOYSA-N diethyl(2-phenylethoxy)silane Chemical compound C(C)[SiH](OCCC1=CC=CC=C1)CC GEIYKBJNMPEXRM-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- KQIXMZWXFFHRAQ-UHFFFAOYSA-N 1-(2-hydroxybutylamino)butan-2-ol Chemical compound CCC(O)CNCC(O)CC KQIXMZWXFFHRAQ-UHFFFAOYSA-N 0.000 description 1
- BFIAIMMAHAIVFT-UHFFFAOYSA-N 1-[bis(2-hydroxybutyl)amino]butan-2-ol Chemical compound CCC(O)CN(CC(O)CC)CC(O)CC BFIAIMMAHAIVFT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- BGGIUGXMWNKMCP-UHFFFAOYSA-N 2-methylpropan-2-olate;zirconium(4+) Chemical compound CC(C)(C)O[Zr](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BGGIUGXMWNKMCP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- KRGXWTOLFOPIKV-UHFFFAOYSA-N 3-(methylamino)propan-1-ol Chemical compound CNCCCO KRGXWTOLFOPIKV-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- QHEICIPYBJHEQV-UHFFFAOYSA-N 4-ethylhex-3-enoxysilane Chemical compound C(C)C(=CCCO[SiH3])CC QHEICIPYBJHEQV-UHFFFAOYSA-N 0.000 description 1
- 229910002976 CaZrO3 Inorganic materials 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940042776 anhydrous calcium iodide Drugs 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- ZXYULJCZWBKBCX-UHFFFAOYSA-N but-1-enyl(diethoxy)silane Chemical compound C(C)C=C[SiH](OCC)OCC ZXYULJCZWBKBCX-UHFFFAOYSA-N 0.000 description 1
- FFOWIEZZYLIBTD-UHFFFAOYSA-N butan-2-olate zirconium(4+) Chemical compound CCC(C)O[Zr](OC(C)CC)(OC(C)CC)OC(C)CC FFOWIEZZYLIBTD-UHFFFAOYSA-N 0.000 description 1
- NPVKWWQBIVSLRO-UHFFFAOYSA-N butan-2-yloxy(trimethyl)silane Chemical compound CCC(C)O[Si](C)(C)C NPVKWWQBIVSLRO-UHFFFAOYSA-N 0.000 description 1
- YTJUXOIAXOQWBV-UHFFFAOYSA-N butoxy(trimethyl)silane Chemical compound CCCCO[Si](C)(C)C YTJUXOIAXOQWBV-UHFFFAOYSA-N 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 229940059251 calcium bromide Drugs 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 1
- QSHXZNJVLUEIHK-UHFFFAOYSA-L calcium;dibromide;hexahydrate Chemical compound O.O.O.O.O.O.[Ca+2].[Br-].[Br-] QSHXZNJVLUEIHK-UHFFFAOYSA-L 0.000 description 1
- YMIFCOGYMQTQBP-UHFFFAOYSA-L calcium;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Ca+2] YMIFCOGYMQTQBP-UHFFFAOYSA-L 0.000 description 1
- ZNLVAQJGGDVQAU-UHFFFAOYSA-L calcium;dichloride;tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Ca+2] ZNLVAQJGGDVQAU-UHFFFAOYSA-L 0.000 description 1
- GVHRTAKEBFEMFD-UHFFFAOYSA-L calcium;diiodide;hexahydrate Chemical compound O.O.O.O.O.O.[Ca+2].[I-].[I-] GVHRTAKEBFEMFD-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- DERJYZOBOMCDCS-UHFFFAOYSA-N di(butan-2-yloxy)-dimethylsilane Chemical compound CCC(C)O[Si](C)(C)OC(C)CC DERJYZOBOMCDCS-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- UYJVWFZJQXTYLG-UHFFFAOYSA-N diethoxy-ethyl-phenylsilane Chemical compound CCO[Si](CC)(OCC)C1=CC=CC=C1 UYJVWFZJQXTYLG-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- BGPNEHJZZDIFND-UHFFFAOYSA-N dimethyl-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)OC(C)(C)C BGPNEHJZZDIFND-UHFFFAOYSA-N 0.000 description 1
- BPXCAJONOPIXJI-UHFFFAOYSA-N dimethyl-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(C)OC(C)C BPXCAJONOPIXJI-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ASBGGHMVAMBCOR-UHFFFAOYSA-N ethanolate;zirconium(4+) Chemical compound [Zr+4].CC[O-].CC[O-].CC[O-].CC[O-] ASBGGHMVAMBCOR-UHFFFAOYSA-N 0.000 description 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- IKGXNCHYONXJSM-UHFFFAOYSA-N methanolate;zirconium(4+) Chemical compound [Zr+4].[O-]C.[O-]C.[O-]C.[O-]C IKGXNCHYONXJSM-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RJNDDRZGJNVASH-UHFFFAOYSA-N tri(butan-2-yloxy)-methylsilane Chemical compound CCC(C)O[Si](C)(OC(C)CC)OC(C)CC RJNDDRZGJNVASH-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-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
- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-UHFFFAOYSA-N 0.000 description 1
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 1
- PGZGBYCKAOEPQZ-UHFFFAOYSA-N trimethyl-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)C PGZGBYCKAOEPQZ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Chemically Coating (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、ZrO2−SiO2−
CaO系コ−ティング組成物に関する。[Industrial Application Field] The present invention relates to ZrO2-SiO2-
The present invention relates to a CaO-based coating composition.
【0002】0002
【従来の技術】従来、金属、プラスチック、木材、紙、
セメント、黒鉛等の素材上に、その耐熱性、耐磨耗性、
耐水性、耐薬品性等を向上させるために、コ−ティング
により塗膜を形成することが行われており、代表的なコ
−ティング方法としては、例えば、シリコン系樹脂をバ
インダ−とする有機塗料によるコ−ティングがあげられ
る。しかしながら、上記有機塗料から得られる塗膜は、
耐熱性に劣り、200℃以上の雰囲気中では長期使用に
耐えることができない。[Prior art] Conventionally, metal, plastic, wood, paper,
On materials such as cement and graphite, its heat resistance, abrasion resistance,
In order to improve water resistance, chemical resistance, etc., coatings are used to form coatings. Typical coating methods include, for example, organic coatings using silicone resin as a binder. An example is coating with paint. However, the coating film obtained from the above organic paint is
It has poor heat resistance and cannot withstand long-term use in an atmosphere of 200°C or higher.
【0003】一方、耐熱性のあるセラミック薄膜を素材
上にコ−ティングすることが提案されており、現在、主
として金属素材に適用されている。上記コ−ティング方
法としては、例えば、蒸着法、スパッタ法、CVD法、
溶射法等があげられるが、上記各コ−ティング方法は、
素材の材質、寸法、形状等に大きな制限があり、しかも
コ−ティング操作が煩雑であるという欠点を有していた
。On the other hand, it has been proposed to coat materials with a heat-resistant ceramic thin film, and this method is currently mainly applied to metal materials. Examples of the coating method include vapor deposition method, sputtering method, CVD method,
Examples include thermal spraying, but each of the above coating methods is
There are major restrictions on the material, size, shape, etc., and the coating operation is complicated.
【0004】上記欠点を解決するために、素材に制限が
なく、しかも種々の大きさ、形状等を有する素材に容易
にコ−ティングしうるジルコン系組成物が提案されてお
り、例えば、特開昭61−250063号公報には、Z
r(OC4H9)4で表されるジルコニウム化合物、エ
チルシリケ−トおよびイソプロピルアルコ−ルを混合し
てなる組成物が記載され、特開昭63−190175号
公報には、ジルコニウムオキシ酸塩、シリコンアルコキ
シドまたはその誘導体、水および有機溶媒からなる組成
物が記載されている。しかしながら、上記組成物は長期
保存安定性が悪く、しかも素材上にコ−ティングして得
られた塗膜は、クラックや剥離を生じ易いという欠点を
有していた。[0004] In order to solve the above-mentioned drawbacks, zircon-based compositions have been proposed that are not limited to materials and can be easily coated on materials having various sizes and shapes. Publication No. 61-250063 states that Z
A composition obtained by mixing a zirconium compound represented by r(OC4H9)4, ethyl silicate, and isopropyl alcohol is described, and JP-A-63-190175 discloses a composition formed by mixing a zirconium compound represented by r(OC4H9)4, ethyl silicate, and isopropyl alcohol. Compositions consisting of its derivatives, water and organic solvents are described. However, the above-mentioned composition had the disadvantage that it had poor long-term storage stability, and the coating film obtained by coating it on the material was prone to cracking and peeling.
【0005】[0005]
【発明が解決しようとする課題】本発明は、上記欠点に
鑑みてなされたものであり、その目的は、容易にコ−テ
ィングができ、安定性に優れた塗膜が得られる長期保存
可能なZrO2−SiO2−CaO系コ−ティング組成
物を提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and its purpose is to provide a coating film that can be easily coated, has excellent stability, and can be stored for a long period of time. An object of the present invention is to provide a ZrO2-SiO2-CaO based coating composition.
【0006】[0006]
【課題を解決するための手段】本発明で使用されるジル
コニウムテトラアルコキシド(a) は、一般式Zr(
OR1)4 で表される化合物であり、式中、R1
はアルキル基を示すが、炭素数が多くなるとZrO2−
SiO2−CaO系コ−ティング組成物の安定性が低下
して長期保存性が悪くなるので、炭素数は1〜5に限定
される。[Means for Solving the Problems] The zirconium tetraalkoxide (a) used in the present invention has the general formula Zr (
It is a compound represented by OR1)4, in which R1
indicates an alkyl group, but as the number of carbon atoms increases, ZrO2-
The number of carbon atoms is limited to 1 to 5, since the stability of the SiO2-CaO coating composition decreases and its long-term storage stability deteriorates.
【0007】上記ジルコニウムテトラアルコキシド(a
) としては、例えば、ジルコニウムテトラメトキシド
、ジルコニウムテトラエトキシド、ジルコニウムテトラ
−n−プロポキシド、ジルコニウムテトラ−iso−プ
ロポキシド、ジルコニウムテトラ−n−ブトキシド、ジ
ルコニウムテトラ−sec−ブトキシド、ジルコニウム
テトラ−tert−ブトキシド等があげられ、特にジル
コニウムテトラ−n−ブトキシドおよびジルコニウムテ
トラ−iso−プロポキシドが好ましい。これらは、単
独で使用されてもよいし二種以上併用されてもよい。The above zirconium tetraalkoxide (a
), for example, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetra-n-propoxide, zirconium tetra-iso-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetra-tert -butoxide, etc., and zirconium tetra-n-butoxide and zirconium tetra-iso-propoxide are particularly preferred. These may be used alone or in combination of two or more.
【0008】本発明で使用されるオルガノアルコキシシ
ラン(b) は、下記の一般式 I 、 II また
は III で表される化合物である。The organoalkoxysilane (b) used in the present invention is a compound represented by the following general formula I, II or III.
【0009】[0009]
【化3】[Chemical formula 3]
【0010】式中、R2 はアルキルを示すが、炭素数
が多くなるとZrO2−SiO2−CaO系コ−ティン
グ組成物の安定性が低下して長期保存性が悪くなるので
、炭素数は1〜5に限定される。R3 、R4 、R5
は有機基を示し、例えば、飽和炭化水素基(アルキル
基、置換アルキル基等)、不飽和炭化水素基(アリル基
、ビニル基等)、芳香族炭化水素基(フェニル基、ナフ
チル基等)、エポキシ基、アミノ基などがあげられる。[0010] In the formula, R2 represents alkyl, but if the number of carbon atoms increases, the stability of the ZrO2-SiO2-CaO coating composition will decrease and long-term storage stability will deteriorate, so the number of carbon atoms should be 1 to 5. limited to. R3, R4, R5
represents an organic group, such as a saturated hydrocarbon group (alkyl group, substituted alkyl group, etc.), an unsaturated hydrocarbon group (allyl group, vinyl group, etc.), an aromatic hydrocarbon group (phenyl group, naphthyl group, etc.), Examples include epoxy groups and amino groups.
【0011】一般式[I]で表される化合物としては、
例えば、モノメチルトリメトキシシラン、モノメチルト
リエトキシシラン、モノメチルトリ−n−プロポキシシ
ラン、モノメチルトリ−iso−プロポキシシラン、モ
ノメチルトリ−n−ブトキシシラン、モノメチルトリ−
sec−ブトキシシラン、モノメチルトリ−tert−
ブトキシシラン、エチルトリエトキシシラン、ビニルト
リエトキシシラン、フェニルトリエトキシシラン、エポ
キシトリエトキシシラン等があげられ、一般式[II]
で表される化合物としては、例えば、ジメチルジメトキ
シシラン、ジメチルジエトキシシラン、ジメチルジ−n
−プロポキシシラン、ジメチルジ−iso−プロポキシ
シラン、ジメチルジ−n−ブトキシシラン、ジメチルジ
−sec−ブトキシシラン、ジメチルジ−tert−ブ
トキシシラン、ジエチルジエトキシシラン、エチルビニ
ルジエトキシシラン、エチルフェニルジエトキシシラン
、メチルエポキシジエトキシシラン等があげられ、一般
式[III ]で表される化合物としては、例えば、ト
リメチルモノメトキシシラン、トリメチルモノエトキシ
シラン、トリメチルモノ−n−プロポキシシラン、トリ
メチルモノ−iso−プロポキシシラン、トリメチルモ
ノ−n−ブトキシシラン、トリメチルモノ−sec−ブ
トキシシラン、トリメチルモノ−tert−ブトキシシ
ラン、トリエチルエトキシシラン、ジエチルビニルエト
キシシラン、ジエチルフェニルエトキシシラン、ジエチ
ルフェニルエトキシシラン、メチルエチルエポキシエト
キシシラン等があげられ、特にモノメチルトリエトキシ
シラン、ビニルトリエトキシシラン、ジメチルジエトキ
シシランおよびジエチルフェニルエトキシシランが好ま
しい。Compounds represented by general formula [I] include:
For example, monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-propoxysilane, monomethyltri-iso-propoxysilane, monomethyltri-n-butoxysilane, monomethyltri-
sec-butoxysilane, monomethyltri-tert-
Examples include butoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, epoxytriethoxysilane, and general formula [II]
Examples of the compound represented by include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n
-Propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldiethoxysilane, ethylvinyldiethoxysilane, ethylphenyldiethoxysilane, methyl Examples of the compound represented by the general formula [III] include epoxydiethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmono-n-propoxysilane, trimethylmono-iso-propoxysilane, Trimethylmono-n-butoxysilane, trimethylmono-sec-butoxysilane, trimethylmono-tert-butoxysilane, triethylethoxysilane, diethylvinylethoxysilane, diethylphenylethoxysilane, diethylphenylethoxysilane, methylethylepoxyethoxysilane, etc. Among them, monomethyltriethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane and diethylphenylethoxysilane are particularly preferred.
【0012】上記オルガノアルコキシシラン(b) は
、単独で使用されてもよいし二種以上併用されてもよい
。上記オルガノアルコキシシラン(b) のジルコニウ
ムテトラアルコキシド(a) に対する添加量は、少な
くなるとZrO2−SiO2−CaO系コ−ティング組
成物の安定性が低下して長期保存性が悪くなり、多くな
ると得られる塗膜にクラックが生じ易くなるので、オル
ガノアルコキシシラン(b) /ジルコニウムテトラア
ルコキシド(a) (モル比)は0.01〜9に限定さ
れ、好ましくは0.1〜6である。The above organoalkoxysilane (b) may be used alone or in combination of two or more. When the amount of the organoalkoxysilane (b) added to the zirconium tetraalkoxide (a) is small, the stability of the ZrO2-SiO2-CaO coating composition is decreased and long-term storage stability is deteriorated, and when it is increased, the amount obtained is Since cracks are likely to occur in the coating film, the molar ratio of organoalkoxysilane (b)/zirconium tetraalkoxide (a) is limited to 0.01 to 9, preferably 0.1 to 6.
【0013】本発明で使用されるカルシウム化合物(c
) は、塩化カルシウム、臭化カルシウムおよび沃化カ
ルシウムからなる群より選ばれる化合物であり、上記カ
ルシウム化合物(c) としては、例えば、無水塩化カ
ルシウム、塩化カルシウム一水塩、塩化カルシウム二水
塩、塩化カルシウム四水塩、塩化カルシウム六水塩、無
水臭化カルシウム、臭化カルシウム六水塩、無水沃化カ
ルシウム、沃化カルシウム六水塩等があげられ、特に無
水塩化カルシウムおよび無水臭化カルシウムが好ましい
。これらは、単独で使用されてもよいし二種以上併用さ
れてもよい。Calcium compound (c
) is a compound selected from the group consisting of calcium chloride, calcium bromide and calcium iodide, and examples of the calcium compound (c) include anhydrous calcium chloride, calcium chloride monohydrate, calcium chloride dihydrate, Examples include calcium chloride tetrahydrate, calcium chloride hexahydrate, anhydrous calcium bromide, calcium bromide hexahydrate, anhydrous calcium iodide, calcium iodide hexahydrate, etc., especially anhydrous calcium chloride and anhydrous calcium bromide. preferable. These may be used alone or in combination of two or more.
【0014】上記カルシウム化合物(c) のジルコニ
ウムテトラアルコキシド(a) に対する添加量は、少
なくなっても、多くなっても得られる塗膜にクラックが
生じやすくなるので、カルシウム化合物(c) /ジル
コニウムテトラアルコキシド(a) (モル比)は0.
01〜9に限定され、好ましくは0.1〜4.0である
。[0014] Even if the amount of the calcium compound (c) added to the zirconium tetraalkoxide (a) is small or large, cracks are likely to occur in the resulting coating film. Alkoxide (a) (molar ratio) is 0.
It is limited to 01 to 9, preferably 0.1 to 4.0.
【0015】本発明で使用されるアミン化合物(d)
は、下記一般式[IV]、[V ] 、[VI]、[
VII ]または[VIII]で表される化合物である
。Amine compound (d) used in the present invention
is represented by the following general formula [IV], [V], [VI], [
VII] or [VIII].
【0016】[0016]
【化4】[C4]
【0017】式中、R3 はアルキレン基を示すが、炭
素数が少なくなっても多くなってもZrO2−SiO2
−CaO系コ−ティング組成物の安定性が低下して長期
保存性が悪くなるので、炭素数は2〜5に限定され、R
4 およびR5 はアルキル基を示すが、炭素数が多く
なるとZrO2−SiO2−CaO系コ−ティング組成
物の安定性が低下して長期保存性が悪くなるので、炭素
数は1〜5に限定される。但し、R5 は水素であって
もよい。In the formula, R3 represents an alkylene group, but whether the number of carbon atoms is small or large, ZrO2-SiO2
Since the stability of the -CaO-based coating composition decreases and its long-term storage property deteriorates, the number of carbon atoms is limited to 2 to 5, and R
4 and R5 represent an alkyl group, but if the number of carbon atoms increases, the stability of the ZrO2-SiO2-CaO-based coating composition will decrease and long-term storage stability will deteriorate, so the number of carbon atoms is limited to 1 to 5. Ru. However, R5 may be hydrogen.
【0018】上記[IV]式で表される化合物としては
、例えば、エタノ−ルアミン、プロパノ−ルアミン、イ
ソプロパノ−ルアミン、ブタノ−ルアミン等があげられ
、[V]式で表される化合物としては、例えば、ジエタ
ノ−ルアミン、ジイソプロパノ−ルアミン、ジブタノ−
ルアミン等あげられ、[VI]式で表される化合物とし
ては、例えば、トリエタノ−ルアミン、トリイソプロパ
ノ−ルアミン、トリブタノ−ルアミン等あげられ、[V
II ]式で表される化合物としては、例えば、N−メ
チルエタノ−ルアミン、N−エチルエタノ−ルアミン、
N−メチルプロパノ−ルアミン、N−エチルプロパノ−
ルアミン、N,N−ジメチルエタノ−ルアミン、N,N
−ジエチルエタノ−ルアミン、N,N−ジブチルエタノ
−ルアミン、N,N−ジメチルプロパノ−ルアミン等が
あげられ、[VIII]式で表される化合物としては、
例えば、N−メチル−N,N−ジエタノ−ルアミン、N
−エチル−N,N−ジエタノ−ルアミン、N−メチル−
N,N−ジイソプロパノ−ルアミン等あげられる。Examples of the compound represented by the above formula [IV] include ethanolamine, propanolamine, isopropanolamine, butanolamine, etc., and the compound represented by the formula [V] includes: For example, diethanolamine, diisopropanolamine, dibutanolamine
Examples of the compound represented by the formula [VI] include triethanolamine, triisopropanolamine, tributanolamine, etc.
II ] Examples of the compound represented by the formula include N-methylethanolamine, N-ethylethanolamine,
N-methylpropanolamine, N-ethylpropanol
amine, N,N-dimethylethanolamine, N,N
-diethylethanolamine, N,N-dibutylethanolamine, N,N-dimethylpropanolamine, etc., and the compound represented by the formula [VIII] is,
For example, N-methyl-N,N-diethanolamine, N
-ethyl-N,N-diethanolamine, N-methyl-
Examples include N,N-diisopropanolamine.
【0019】上記アミン化合物(d) のジルコニウム
テトラアルコキシド(a) に対する添加量は、少なく
なるとZrO2−SiO2−CaO系コ−ティング組成
物の安定性が低下して長期保存性が悪くなり、多くなる
と得られる塗膜にクラックが生じやすくなるので、アミ
ン化合物(d) /ジルコニウムテトラアルコキシド(
a) (モル比)は0.5〜6に限定される。If the amount of the amine compound (d) added to the zirconium tetraalkoxide (a) is too small, the stability of the ZrO2-SiO2-CaO coating composition will deteriorate, resulting in poor long-term storage stability; Since cracks are likely to occur in the resulting coating film, amine compound (d)/zirconium tetraalkoxide (
a) (Molar ratio) is limited to 0.5-6.
【0020】本発明に使用される有機溶媒(e) は、
前記ジルコニウムテトラアルコキシド(a) およびオ
ルガノアルコキシシラン(b) と相溶性があり、カル
シウム化合物(c)が溶解性を示すものであれば特に限
定されるものではなく、例えば、メチルアルコ−ル、エ
チルアルコ−ル、イソプロピルアルコ−ル、ブチルアル
コ−ル等のアルコ−ル類、アセトン、メチルエチルケト
ン等のケトン類、テトラヒドロフランなどがあげられ、
特にエタノ−ル、イソプロピルアルコ−ルが好ましい。
これらは単独で使用されてもよいし二種以上併用されて
もよい。The organic solvent (e) used in the present invention is:
It is not particularly limited as long as it is compatible with the zirconium tetraalkoxide (a) and organoalkoxysilane (b) and shows solubility in the calcium compound (c). For example, methyl alcohol, ethyl alcohol, etc. Examples include alcohols such as alcohol, isopropyl alcohol, and butyl alcohol, ketones such as acetone and methyl ethyl ketone, and tetrahydrofuran.
Particularly preferred are ethanol and isopropyl alcohol. These may be used alone or in combination of two or more.
【0021】上記有機溶媒(e) の添加量は、少なく
なるとZrO2−SiO2−CaO系コ−ティング組成
物の安定性が低下して長期保存性が悪くなり、多くなる
と得られる塗膜にピンホ−ルが生じやすくなるので、有
機溶媒(d) /〔ジルコニウムテトラアルコキシド(
a) +オルガノアルコキシシラン(b) 〕(モル比
)は0. 05〜500であり、好ましくはは0. 2
〜300である。[0021] If the amount of the organic solvent (e) added is too small, the stability of the ZrO2-SiO2-CaO coating composition will be reduced, resulting in poor long-term storage stability, and if it is too large, pinholes will appear in the resulting coating film. organic solvent (d) / [zirconium tetraalkoxide (
a) +organoalkoxysilane (b)] (molar ratio) is 0. 05 to 500, preferably 0.05 to 500, preferably 0. 2
~300.
【0022】本発明のZrO2−SiO2−CaO系コ
−ティング組成物の製造方法としては特に限定されるも
のではなく、例えば、上述した構成材料を一括して混合
する方法、特定の構成材料を分割して混合した後、残り
の構成材料を添加して混合する方法等があげられるが、
後者の方法が好ましく、例えば、特定の構成材料として
ジルコニウムテトラアルコキシド(a) 、アミン化合
物(d) および有機溶媒(e) を混合した後、オル
ガノアルコキシシラン(b) およびカルシウム化合物
(c) を添加する方法が採用される。The method for producing the ZrO2-SiO2-CaO-based coating composition of the present invention is not particularly limited. After mixing, the remaining constituent materials are added and mixed.
The latter method is preferred; for example, after mixing zirconium tetraalkoxide (a), amine compound (d) and organic solvent (e) as specific constituent materials, organoalkoxysilane (b) and calcium compound (c) are added. The method will be adopted.
【0023】本発明のZrO2−SiO2−CaO系コ
−ティング組成物の構成は上述した通りであるが、全ア
ルコキシド(ジルコニウムテトラアルコキシド(a)
とオルガノアルコキシシラン(b) )の加水分解を促
進し、塗膜の形成を容易にするために、水、酸、アルカ
リ等が添加されてもよい。The composition of the ZrO2-SiO2-CaO coating composition of the present invention is as described above, except that all alkoxides (zirconium tetraalkoxide (a)
Water, acid, alkali, etc. may be added to promote the hydrolysis of and organoalkoxysilane (b) and facilitate the formation of a coating film.
【0024】また、得られる塗膜の安定性(耐クラック
性、耐剥離性等)をさらに向上させるためにZr、Si
、Ca等の酸化物粉末(例えば、ZrO2 、SiO2
、CaO、CaZrO3 、ZrSiO4 、Ca3
Si2ZrO9 等の粉末)が添加されてもよい。[0024] In order to further improve the stability (crack resistance, peeling resistance, etc.) of the resulting coating film, Zr, Si
, Ca, etc. oxide powder (e.g. ZrO2, SiO2
, CaO, CaZrO3, ZrSiO4, Ca3
Powder such as Si2ZrO9) may be added.
【0025】上記酸化物粉末の平均粒径は、小さくなる
とZrO2−SiO2−CaO系コ−ティング組成物中
への分散が困難になり、大きくなると得られる塗膜にク
ラックが生じやすくなるので、0. 01〜100μm
が好ましく、0. 02〜10μmが特に好ましい。[0025] The average particle size of the oxide powder should be set to 0 because if it becomes small, it becomes difficult to disperse it into the ZrO2-SiO2-CaO coating composition, and if it becomes large, cracks are likely to occur in the resulting coating film. .. 01~100μm
is preferable, and 0. Particularly preferred is 02 to 10 μm.
【0026】上記酸化物粉末のZrO2−SiO2−C
aO系コ−ティング組成物中への添加量は、少なくなる
と得られる塗膜の安定性の向上の度合いが低くなり、多
くなるとZrO2−SiO2−CaO系コ−ティング組
成物の安定性が低下して長期保存性が悪くなるので、全
ZrO2−SiO2−CaO系酸化物(ジルコニウムテ
トラアルコキシド(a) 、オルガノアルコキシシラン
(b) およびカルシウム化合物(c) から形成され
る酸化物および上記酸化物粉末の合計量)中1〜60重
量%が好ましい。なお、酸化物粉末の添加は、前記Zr
O2−SiO2−CaO系コ−ティング組成物の各構成
材料を混合した後になされるのが好ましい。ZrO2-SiO2-C of the above oxide powder
If the amount added to the aO-based coating composition is small, the degree of improvement in the stability of the resulting coating film will be low, and if it is too large, the stability of the ZrO2-SiO2-CaO-based coating composition will be reduced. Therefore, all ZrO2-SiO2-CaO-based oxides (oxides formed from zirconium tetraalkoxide (a), organoalkoxysilane (b) and calcium compound (c) and the above oxide powders) The total amount is preferably 1 to 60% by weight. Note that the addition of the oxide powder
Preferably, this is done after mixing the constituent materials of the O2-SiO2-CaO based coating composition.
【0027】本発明のZrO2−SiO2−CaO系コ
−ティング組成物は、前記素材に塗布または含浸され、
乾燥されてZrO2−SiO2−CaO系酸化物被膜が
形成される。上記塗布方法としては特に限定されるもの
ではなく、例えば、刷毛、スプレ−コ−ト、ディップコ
−ト、スピンコ−ト、ロ−ルコ−ト等による塗布方法が
あげられる。[0027] The ZrO2-SiO2-CaO based coating composition of the present invention is applied or impregnated onto the above material,
After drying, a ZrO2-SiO2-CaO-based oxide film is formed. The above-mentioned coating method is not particularly limited, and examples thereof include coating methods such as brush coating, spray coating, dip coating, spin coating, and roll coating.
【0028】上記含浸方法としては特に限定されるもの
ではなく、例えば、常圧下で浸漬含浸する方法、減圧下
で浸漬含浸する方法等があげられ、減圧下で浸漬含浸す
るのが好ましい。The above-mentioned impregnation method is not particularly limited, and includes, for example, a method of impregnation by immersion under normal pressure, a method of impregnation by immersion under reduced pressure, etc., and impregnation by immersion under reduced pressure is preferred.
【0029】上記乾燥方法としては特に限定されるもの
ではなく、室温にて自然乾燥してもよいし、加熱乾燥し
てもよい。また、乾燥した後、必要に応じて、高温加熱
処理してもよい。The drying method described above is not particularly limited, and may be natural drying at room temperature or heating drying. Moreover, after drying, high-temperature heat treatment may be performed as necessary.
【0030】[0030]
【実施例】以下、本発明の実施例を説明する。なお、結
果に示したZrO2−SiO2−CaO系コ−ティング
組成物に関する各物性の評価方法は次の通りである。[Examples] Examples of the present invention will be described below. The evaluation method for each physical property of the ZrO2-SiO2-CaO coating composition shown in the results is as follows.
【0031】(1) 初期密着性
得られたZrO2−SiO2−CaO系コ−ティング組
成物中に、アセトンで超音波洗浄したスライドガラス(
マツナミ社製)を浸漬し、300mm/分の速度で引上
げた後、下記条件下で乾燥して、ZrO2−SiO2−
CaO系酸化物被覆層を形成して評価試料を作製し、J
IS D 0202に準じてクロスカットテ−プ剥離試
験を行い、100個のZrO2−SiO2−CaO系酸
化物被覆層の枡目に対する残存した枡目の比率(密着率
)を測定して評価した。(1) Initial adhesion A slide glass (
Matsunami Co., Ltd.) was immersed in the ZrO2-SiO2-
An evaluation sample was prepared by forming a CaO-based oxide coating layer, and J
A cross-cut tape peeling test was conducted according to IS D 0202, and the ratio of the remaining squares to the squares of 100 ZrO2-SiO2-CaO-based oxide coating layers (adhesion rate) was measured and evaluated.
【0032】(乾燥条件)
初期乾燥:25℃、24時間
最終乾燥:500℃(25℃から50℃/hrで昇温)
、2時間保持(Drying conditions) Initial drying: 25°C, 24 hours Final drying: 500°C (temperature raised from 25°C at 50°C/hr)
, held for 2 hours
【0033】(2) 鉛筆硬度
得られたZrO2−SiO2−CaO系コ−ティング組
成物を用いて、上記初期密着性を評価したのと同様にし
て評価試料を作製し、JISK 5400に準じて測定
した。(2) Pencil hardness Using the obtained ZrO2-SiO2-CaO based coating composition, an evaluation sample was prepared in the same manner as in the above evaluation of initial adhesion, and measured according to JISK 5400. did.
【0034】(3) 耐沸騰水性(耐クラック性および
密着耐久性)
得られたZrO2−SiO2−CaO系コ−ティング組
成物を用いて、上記初期密着性を評価したのと同様にし
て作製した評価試料を沸騰水中に8時間浸漬した後、そ
の表面の状態を官能検査して下記判定基準により耐クラ
ック性を評価した。(3) Boiling Water Resistance (Crack Resistance and Adhesion Durability) Using the obtained ZrO2-SiO2-CaO based coating composition, a film was prepared in the same manner as in the above evaluation of initial adhesion. After the evaluation sample was immersed in boiling water for 8 hours, the state of its surface was subjected to a sensory test and the crack resistance was evaluated according to the following criteria.
【0035】(判定基準)
○:表面にクラックなし
×:表面にクラックあり
上記官能検査を行った後、上記初期密着性を評価したの
と同様にしてクロスカットテ−プ剥離試験を行い、密着
率により密着耐久性を評価した。(Judgment Criteria) ○: No cracks on the surface ×: Cracks on the surface After performing the above sensory test, a cross-cut tape peeling test was performed in the same manner as in the above initial adhesion evaluation, and the adhesion was confirmed. The adhesion durability was evaluated based on the ratio.
【0036】(4) 耐酸性(耐クラック性および密着
耐久性)
得られたZrO2−SiO2−CaO系コ−ティング組
成物を用いて、上記初期密着性を評価したのと同様にし
て作製した評価試料を20wt%の塩酸中に75時間浸
漬した後、その表面の状態を官能検査して下記判定基準
により耐クラック性を評価した。(4) Acid resistance (crack resistance and adhesion durability) Evaluation made using the obtained ZrO2-SiO2-CaO coating composition in the same manner as in the above initial adhesion evaluation. After the sample was immersed in 20 wt % hydrochloric acid for 75 hours, the state of the surface thereof was subjected to a sensory test and the crack resistance was evaluated according to the following criteria.
【0037】(判定基準)
○:表面にクラックなし
×:表面にクラックあり
上記官能検査を行った後、上記初期密着性を評価したの
と同様にしてクロスカットテ−プ剥離試験を行い、密着
率により密着耐久性を評価した。(Judgment Criteria) ○: No cracks on the surface ×: Cracks on the surface After performing the above sensory test, a cross-cut tape peeling test was performed in the same manner as in the above initial adhesion evaluation, and adhesion was determined. The adhesion durability was evaluated based on the ratio.
【0038】(5) 長期保存性
得られたZrO2−SiO2−CaO系コ−ティング組
成物が封入された密封容器を50℃、65%RHの雰囲
気下に3ヶ月放置した後、上記初期密着性を評価したの
と同様にして評価試料を作製し、クロスカットテ−プ剥
離試験を行い、下記判定基準により長期保存性を評価し
た。(5) Long-term storage property After the sealed container containing the obtained ZrO2-SiO2-CaO coating composition was left in an atmosphere of 50° C. and 65% RH for 3 months, the above-mentioned initial adhesion was confirmed. An evaluation sample was prepared in the same manner as in the evaluation, a cross-cut tape peeling test was conducted, and long-term storage stability was evaluated according to the following criteria.
【0039】(判定基準) ○:密着率が80%を超えるもの ×:密着率が80%以下のもの(Judgment criteria) ○: Adhesion rate exceeds 80% ×: Adhesion rate is 80% or less
【0040】(実施例1〜13)表1に示した所定量の
ジルコニウムテトラアルコキシド、アミン化合物(一般
式[IV]、[V ]または[VI]で表される化合物
)およびエチルアルコ−ルをセパラブルフラスコに供給
し、室温で15時間、攪拌速度800rpm で攪拌し
て安定化されたジルコニウムテトラアルコキシドのアル
コ−ル溶液を得た。(Examples 1 to 13) Predetermined amounts of zirconium tetraalkoxide shown in Table 1, amine compound (compound represented by general formula [IV], [V] or [VI]) and ethyl alcohol were separated. The mixture was supplied to a bull flask and stirred at room temperature for 15 hours at a stirring speed of 800 rpm to obtain a stabilized alcoholic solution of zirconium tetraalkoxide.
【0041】得られたアルコ−ル溶液に表1に示した所
定量のオルガノアルコキシシランを添加し、室温で5時
間、攪拌速度800rpm で攪拌し、得られた溶液に
表1に示した所定量のカルシウム化合物を添加し、室温
で24時間、攪拌速度800rpmで攪拌してZrO2
−SiO2−CaO系コ−ティング組成物を得た。[0041] The predetermined amount of organoalkoxysilane shown in Table 1 was added to the obtained alcohol solution, and the mixture was stirred at room temperature for 5 hours at a stirring speed of 800 rpm. of calcium compound and stirred at room temperature for 24 hours at a stirring speed of 800 rpm to form ZrO2.
A -SiO2-CaO based coating composition was obtained.
【0042】得られたZrO2−SiO2−CaO系コ
−ティング組成物を用いて、前記測定法に基づき、各物
性を測定し、結果を表1に示した。Using the obtained ZrO2-SiO2-CaO based coating composition, various physical properties were measured based on the measurement method described above, and the results are shown in Table 1.
【0043】(実施例14)実施例1において、塩酸水
溶液(濃度:3モル/l)を1モル当量加えた以外は、
実施例1と同様にしてZrO2−SiO2−CaO系コ
−ティング組成物を得た。得られたZrO2−SiO2
−CaO系コ−ティング組成物を用いて、前記測定法に
基づき、各物性を測定し、結果を表1に示した。(Example 14) In Example 1, except that 1 molar equivalent of an aqueous hydrochloric acid solution (concentration: 3 mol/l) was added.
A ZrO2-SiO2-CaO based coating composition was obtained in the same manner as in Example 1. Obtained ZrO2-SiO2
Using the -CaO-based coating composition, each physical property was measured based on the measurement method described above, and the results are shown in Table 1.
【0044】(実施例15)表1に示した通り、エチル
アルコ−ルの添加量を変えた以外は実施例1と同様にし
てZrO2−SiO2−CaO系コ−ティング組成物を
得た。(Example 15) As shown in Table 1, a ZrO2-SiO2-CaO based coating composition was obtained in the same manner as in Example 1 except that the amount of ethyl alcohol added was changed.
【0045】得られたZrO2−SiO2−CaO系コ
−ティング組成物に、全ZrO2−SiO2−CaO系
酸化物(ジルコニウムテトラアルコキシド、オルガノア
ルコキシシランおよびカルシウム化合物から形成される
酸化物、ならびにCa3Si2ZrO9 粉末の合計量
)中40重量%に相当する量のCa3Si2ZrO9
粉末(平均粒径1μm)を添加し、室温で1時間、攪拌
速度1000rpm で攪拌してCa3Si2ZrO9
粉末含有ZrO2−SiO2−CaO系コ−ティング
組成物を得た。[0045] The obtained ZrO2-SiO2-CaO-based coating composition was coated with all ZrO2-SiO2-CaO-based oxides (oxides formed from zirconium tetraalkoxide, organoalkoxysilane and calcium compounds, and Ca3Si2ZrO9 powder). Ca3Si2ZrO9 in an amount corresponding to 40% by weight in the total amount)
Powder (average particle size 1 μm) was added and stirred at room temperature for 1 hour at a stirring speed of 1000 rpm to form Ca3Si2ZrO9.
A powder-containing ZrO2-SiO2-CaO coating composition was obtained.
【0046】得られたCa3Si2ZrO9 粉末含有
ZrO2−SiO2−CaO系コ−ティング組成物を用
いて、前記測定法に基づき、各物性を測定し、結果を表
1に示した。Using the obtained ZrO2-SiO2-CaO coating composition containing Ca3Si2ZrO9 powder, various physical properties were measured based on the measurement method described above, and the results are shown in Table 1.
【0047】[0047]
【表1】[Table 1]
【0048】(比較例1〜6)表2に示した所定量のジ
ルコニウムテトラアルコキシド、アミン化合物(一般式
[IV]、[V ]または[VI]で表される化合物)
、エチルアルコ−ル、オルガノアルコキシシランおよび
カルシウム化合物を用い、実施例1と同様にしてZrO
2−SiO2−CaO系コ−ティング組成物を得た。得
られたZrO2−SiO2−CaO系コ−ティング組成
物を用いて、前記測定法に基づき、各物性を測定し、結
果を表2に示した。(Comparative Examples 1 to 6) Predetermined amounts of zirconium tetraalkoxide and amine compounds shown in Table 2 (compounds represented by general formula [IV], [V] or [VI])
, ethyl alcohol, organoalkoxysilane and a calcium compound in the same manner as in Example 1.
A 2-SiO2-CaO based coating composition was obtained. Using the obtained ZrO2-SiO2-CaO based coating composition, various physical properties were measured based on the measurement method described above, and the results are shown in Table 2.
【0049】[0049]
【表2】[Table 2]
【0050】(実施例16〜25、比較例7〜10)表
3に示した所定量のジルコニウムテトラアルコキシド、
アミン化合物(一般式[VII ]または[VIII]
で表される化合物)およびエチルアルコ−ルをセパラブ
ルフラスコに供給し、室温で15時間、攪拌速度800
rpm で攪拌して安定化されたジルコニウムテトラア
ルコキシドのアルコ−ル溶液を得た。(Examples 16 to 25, Comparative Examples 7 to 10) Predetermined amounts of zirconium tetraalkoxide shown in Table 3,
Amine compound (general formula [VII] or [VIII]
A compound represented by ) and ethyl alcohol were supplied to a separable flask, and stirred at room temperature for 15 hours at a stirring speed of 800.
A stabilized alcoholic solution of zirconium tetraalkoxide was obtained by stirring at rpm.
【0051】得られたアルコ−ル溶液に表3に示した所
定量のオルガノアルコキシシランを添加し、室温で5時
間、攪拌速度800rpm で攪拌し、得られた溶液に
表3に示した所定量のカルシウム化合物を添加し、室温
で24時間、攪拌速度800rpmで攪拌してZrO2
−SiO2−CaO系コ−ティング組成物を得た。[0051] The predetermined amount of organoalkoxysilane shown in Table 3 was added to the obtained alcohol solution, and the mixture was stirred at room temperature for 5 hours at a stirring speed of 800 rpm. of calcium compound and stirred at room temperature for 24 hours at a stirring speed of 800 rpm to form ZrO2.
A -SiO2-CaO based coating composition was obtained.
【0052】得られたZrO2−SiO2−CaO系コ
−ティング組成物を用いて、前記測定法に基づき、各物
性を測定し、結果を表3に示した。Using the obtained ZrO2-SiO2-CaO based coating composition, various physical properties were measured based on the measurement method described above, and the results are shown in Table 3.
【0053】[0053]
【表3】[Table 3]
【0054】[0054]
【発明の効果】本発明のZrO2−SiO2−CaO系
コ−ティング組成物の構成は前記した通りであり、特定
のアミン化合物で安定化されたジルコニウムテトラアル
コキシド、オルガノアルコキシシラン、カルシウム化合
物および有機溶媒が特定量配合されているから、長期間
保存可能であり、かつ金属、プラスチック、木材、紙、
セメント、黒鉛等の種々の素材上に耐熱性、耐磨耗性、
耐水性、耐薬品性に優れる塗膜が容易に形成できる。Effects of the Invention The composition of the ZrO2-SiO2-CaO-based coating composition of the present invention is as described above, and includes a zirconium tetraalkoxide stabilized with a specific amine compound, an organoalkoxysilane, a calcium compound, and an organic solvent. Contains a specific amount of
Heat resistant, abrasion resistant, etc. on various materials such as cement and graphite.
A coating film with excellent water resistance and chemical resistance can be easily formed.
Claims (1)
中、R1 は炭素数1〜5のアルキル基を示す)で表さ
れるジルコニウムテトラアルコキシド、(b) 下記の
一般式[I]、[II]または[III ]で表される
オルガノアルコキシシラン、 【化1】 (式中、R2 は炭素数1〜5のアルキル基、R3 、
R4 、R5 は有機基) (c) 塩化カルシウム、臭化カルシウムおよび沃化カ
ルシウムからなる群より選ばれるカルシウム化合物、(
d) 下記一般式[IV]、[V ]、[VI]、[V
II ]または[VIII]で表されるアミン化合物、
ならびに【化2】 (式中、R6 は炭素数2〜5のアルキレン基、R7
は炭素数1〜5のアルキル基、R8 は炭素数1〜5の
アルキル基または水素を示す) (e) 有機溶媒 よりなり、上記各成分のモル比が、(b) /(a)
=0. 01〜9、(c) /(a) =0. 01〜
9、(d) /(a) =0. 5〜6および((e)
/(a) +(b) )=0. 05〜500である
ことを特徴とするZrO2−SiO2−CaO系コ−テ
ィング組成物。Claim 1: (a) a zirconium tetraalkoxide represented by the general formula Zr(OR1)4 (in the formula, R1 represents an alkyl group having 1 to 5 carbon atoms), (b) a zirconium tetraalkoxide represented by the following general formula [I] , [II] or [III], [Formula 1] (wherein, R2 is an alkyl group having 1 to 5 carbon atoms, R3 is
R4 and R5 are organic groups) (c) a calcium compound selected from the group consisting of calcium chloride, calcium bromide and calcium iodide;
d) The following general formulas [IV], [V ], [VI], [V
amine compound represented by [II] or [VIII],
and [Formula 2] (wherein, R6 is an alkylene group having 2 to 5 carbon atoms, R7
is an alkyl group having 1 to 5 carbon atoms, and R8 is an alkyl group having 1 to 5 carbon atoms or hydrogen.
=0. 01-9, (c) / (a) =0. 01~
9, (d) / (a) =0. 5-6 and ((e)
/(a)+(b))=0. 05 to 500.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7516891A JPH04310584A (en) | 1991-04-08 | 1991-04-08 | Zro2-sio2-cao-based coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7516891A JPH04310584A (en) | 1991-04-08 | 1991-04-08 | Zro2-sio2-cao-based coating composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04310584A true JPH04310584A (en) | 1992-11-02 |
Family
ID=13568404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7516891A Pending JPH04310584A (en) | 1991-04-08 | 1991-04-08 | Zro2-sio2-cao-based coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04310584A (en) |
-
1991
- 1991-04-08 JP JP7516891A patent/JPH04310584A/en active Pending
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