JP7545871B2 - Watch components and their manufacturing method, movement and watch - Google Patents
Watch components and their manufacturing method, movement and watch Download PDFInfo
- Publication number
- JP7545871B2 JP7545871B2 JP2020196739A JP2020196739A JP7545871B2 JP 7545871 B2 JP7545871 B2 JP 7545871B2 JP 2020196739 A JP2020196739 A JP 2020196739A JP 2020196739 A JP2020196739 A JP 2020196739A JP 7545871 B2 JP7545871 B2 JP 7545871B2
- Authority
- JP
- Japan
- Prior art keywords
- sol
- watch
- inorganic
- polymer material
- inorganic polymer
- 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.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920000592 inorganic polymer Polymers 0.000 claims description 74
- 239000002861 polymer material Substances 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000003086 colorant Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 81
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 21
- 239000010949 copper Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 230000005291 magnetic effect Effects 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 2
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-N 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- CEZCCHQBSQPRMU-LLIZZRELSA-L Allura red AC Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1\N=N\C1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-LLIZZRELSA-L 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- 244000017106 Bixa orellana Species 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 240000004160 Capsicum annuum Species 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 244000020518 Carthamus tinctorius Species 0.000 description 1
- 235000003255 Carthamus tinctorius Nutrition 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- IGXWBGJHJZYPQS-SSDOTTSWSA-N D-Luciferin Chemical compound OC(=O)[C@H]1CSC(C=2SC3=CC=C(O)C=C3N=2)=N1 IGXWBGJHJZYPQS-SSDOTTSWSA-N 0.000 description 1
- CYCGRDQQIOGCKX-UHFFFAOYSA-N Dehydro-luciferin Natural products OC(=O)C1=CSC(C=2SC3=CC(O)=CC=C3N=2)=N1 CYCGRDQQIOGCKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000000940 FEMA 2235 Substances 0.000 description 1
- 239000004214 Fast Green FCF Substances 0.000 description 1
- RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
- BJGNCJDXODQBOB-UHFFFAOYSA-N Fivefly Luciferin Natural products OC(=O)C1CSC(C=2SC3=CC(O)=CC=C3N=2)=N1 BJGNCJDXODQBOB-UHFFFAOYSA-N 0.000 description 1
- 244000111489 Gardenia augusta Species 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- DDWFXDSYGUXRAY-UHFFFAOYSA-N Luciferin Natural products CCc1c(C)c(CC2NC(=O)C(=C2C=C)C)[nH]c1Cc3[nH]c4C(=C5/NC(CC(=O)O)C(C)C5CC(=O)O)CC(=O)c4c3C DDWFXDSYGUXRAY-UHFFFAOYSA-N 0.000 description 1
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 description 1
- 229930182559 Natural dye Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- OIQPTROHQCGFEF-QIKYXUGXSA-L Sunset Yellow FCF Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-QIKYXUGXSA-L 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012741 allura red AC Nutrition 0.000 description 1
- 239000004191 allura red AC Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 235000012735 amaranth Nutrition 0.000 description 1
- 239000004178 amaranth Substances 0.000 description 1
- 235000012665 annatto Nutrition 0.000 description 1
- 239000010362 annatto Substances 0.000 description 1
- 235000010208 anthocyanin Nutrition 0.000 description 1
- 239000004410 anthocyanin Substances 0.000 description 1
- 229930002877 anthocyanin Natural products 0.000 description 1
- 150000004636 anthocyanins Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- 239000004161 brilliant blue FCF Substances 0.000 description 1
- 229940055580 brilliant blue fcf Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001511 capsicum annuum Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 239000004106 carminic acid Substances 0.000 description 1
- 150000001746 carotenes Chemical class 0.000 description 1
- 235000005473 carotenes Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940080423 cochineal Drugs 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002889 diamagnetic material Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-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
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- 235000012732 erythrosine Nutrition 0.000 description 1
- 239000004174 erythrosine Substances 0.000 description 1
- 229940011411 erythrosine Drugs 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical group [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical group [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019240 fast green FCF Nutrition 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002212 flavone derivatives Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000007946 flavonol Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- 229960003988 indigo carmine Drugs 0.000 description 1
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 235000012738 indigotine Nutrition 0.000 description 1
- 239000004179 indigotine Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 150000002739 metals Chemical class 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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PYUYQYBDJFMFTH-WMMMYUQOSA-N naphthol red Chemical compound CCOC1=CC=CC=C1NC(=O)C(C1=O)=CC2=CC=CC=C2\C1=N\NC1=CC=C(C(N)=O)C=C1 PYUYQYBDJFMFTH-WMMMYUQOSA-N 0.000 description 1
- 239000000978 natural dye Substances 0.000 description 1
- 229940048276 new coccine Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000012731 ponceau 4R Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940026314 red yeast rice Drugs 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 235000012751 sunset yellow FCF Nutrition 0.000 description 1
- 239000004173 sunset yellow FCF Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- OVTCUIZCVUGJHS-VQHVLOKHSA-N trans-dipyrrin Chemical compound C=1C=CNC=1/C=C1\C=CC=N1 OVTCUIZCVUGJHS-VQHVLOKHSA-N 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 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
Images
Classifications
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B13/00—Gearwork
- G04B13/02—Wheels; Pinions; Spindles; Pivots
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B15/00—Escapements
- G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、時計用部品とその製造方法、ムーブメントおよび時計に関する。 The present invention relates to watch components and their manufacturing methods, movements, and watches.
腕時計を構成する部品は、一般的に炭素鋼や真鍮等の金属材料を加工したものである。時計の精度を向上させる方法として、部品の軽量化や非磁性化が有効であることが知られている。
例えば特許文献１には、母体が軽量非金属素材である単結晶シリコンで構成され、その表面全体を金属とシリコンとの合金膜、または酸化膜と合金層との積層膜で被覆した部品が開示されている。
The components that make up a wristwatch are generally made of processed metal materials such as carbon steel, brass, etc. It is known that reducing the weight of components and making them non-magnetic are effective methods for improving the accuracy of a watch.
For example, Patent Document 1 discloses a component whose base body is made of single crystal silicon, a lightweight non-metallic material, and whose entire surface is covered with an alloy film of metal and silicon, or a laminated film of an oxide film and an alloy layer.
しかし、シリコンは脆性材料であることから、シリコンを時計用部品として用いる場合には、特許文献１に記載されているように、シリコンからなる母体の表面を合金膜、または酸化膜と合金膜との積層膜で被覆する必要があり、手間がかかる。
そのため、シリコン部品に代わる、軽量化および非磁性化が可能な時計用部品が求められている。
However, because silicon is a brittle material, when using silicon as a watch component, as described in Patent Document 1, the surface of a silicon substrate needs to be coated with an alloy film or a laminated film of an oxide film and an alloy film, which is time-consuming.
Therefore, there is a demand for lighter, non-magnetic watch components to replace silicon components.
本発明の一態様は、軽量化および非磁性化が可能な時計用部品、ムーブメントおよび時計を提供することを目的とする。
本発明の一態様は、軽量化および非磁性化が可能な時計用部品を簡易に製造できる時計用部品の製造方法を提供することを目的とする。
An object of one aspect of the present invention is to provide a timepiece component, movement, and timepiece that can be made lightweight and non-magnetic.
An object of one aspect of the present invention is to provide a method for manufacturing a timepiece component that can easily produce a timepiece component that can be made lightweight and non-magnetic.
本発明の一態様は、無機元素（Ｍｅ）と酸素（Ｏ）とを含む無機高分子材からなる、時計用部品を提供する。
この構成によれば、軽量化および非磁性化が可能となる。
One aspect of the present invention provides a watch component made of an inorganic polymer material containing an inorganic element (Me) and oxygen (O).
This configuration allows for weight reduction and non-magnetic design.
前記無機元素（Ｍｅ）と前記酸素（Ｏ）とのモル比（Ｍｅ：Ｏ）が１：２～１：１であることが好ましい。
この構成によれば、無機高分子材が適度な硬さとなる。よって、本発明の時計用部品をある程度の硬さが求められる部品、例えばがんぎ歯車部やアンクル体として最適に使用できる。
The molar ratio (Me:O) of the inorganic element (Me) to the oxygen (O) is preferably 1:2 to 1:1.
This structure gives the inorganic polymer material an appropriate hardness, making the timepiece component of the present invention ideal for use as a component that requires a certain degree of hardness, such as an escape wheel portion or an anchor body.
前記無機高分子材がアルキル基をさらに含むことが好ましい。 It is preferable that the inorganic polymer further contains an alkyl group.
前記無機高分子材がフッ素樹脂をさらに含むことが好ましい。
この構成によれば、摺動時にフッ素樹脂が時計用部品の表面に露出しやすくなり、耐摩耗性が向上する。
It is preferable that the inorganic polymer material further contains a fluororesin.
With this configuration, the fluororesin is more likely to be exposed on the surface of the timepiece component during sliding, improving wear resistance.
前記無機高分子材が無機粉末をさらに含むことが好ましい。
前記無機粉末が前記無機高分子材中で等間隔に分散していることが好ましい。
この構成によれば、ゾルゲル反応領域を減らすことができるので成形時（ゾルの硬化時）の収縮量を低減でき、ヒケを抑制できる。特に、無機粉末が無機高分子材中で等間隔に分散していれば、ブラッグの法則により光の特定波長が反射し、時計用部品が着色しているように見え、外観が向上する。
It is preferable that the inorganic polymer material further contains an inorganic powder.
It is preferable that the inorganic powder is dispersed at equal intervals in the inorganic polymer material.
According to this configuration, the sol-gel reaction area can be reduced, so the amount of shrinkage during molding (when the sol hardens) can be reduced, and sink marks can be suppressed. In particular, if the inorganic powder is dispersed at equal intervals in the inorganic polymer material, specific wavelengths of light are reflected according to Bragg's law, making the watch parts appear colored, improving their appearance.
前記無機高分子材が着色剤をさらに含むことが好ましい。
この構成によれば、時計用部品が着色するので、外観が向上する。
It is preferable that the inorganic polymer material further contains a colorant.
According to this configuration, the timepiece component is colored, improving its appearance.
前記無機高分子材が無色透明であることが好ましい。
前記時計用部品は、インサート成形品であってもよい。
無機高分子材が無色透明であれば、本発明の時計用部品を例えばミステリーウォッチ用の部品としても適用できる。
The inorganic polymer material is preferably colorless and transparent.
The timepiece part may be an insert molding.
If the inorganic polymer material is colorless and transparent, the timepiece part of the present invention can also be used as a part for a mystery watch, for example.
本発明の一態様は、前記時計用部品を備えたムーブメントを提供する。
この構成によれば、前記時計用部品を備えているため、軽量である。
One aspect of the present invention provides a movement equipped with the above-mentioned timepiece component.
According to this configuration, since the watch includes the timepiece component, the watch is lightweight.
本発明の一態様は、前記ムーブメントを備えた時計を提供する。
この構成によれば、前記時計用部品を備えているため、軽量である。
One aspect of the present invention provides a timepiece equipped with the above movement.
According to this configuration, since the watch includes the timepiece component, the watch is lightweight.
本発明の一態様は、無機元素（Ｍｅ）およびアルコキシ基を含む化合物と、水と、触媒とを含む混合物を加熱してゾルを得た後に、得られたゾルを加熱して硬化する、時計用部品の製造方法を提供する。
この構成によれば、軽量化および非磁性化が可能な時計用部品を簡易に製造できる。
One aspect of the present invention provides a method for producing a watch component, comprising heating a mixture containing an inorganic element (Me) and an alkoxy group-containing compound, water, and a catalyst to obtain a sol, and then heating the obtained sol to harden it.
This configuration makes it possible to easily manufacture a timepiece component that is lightweight and non-magnetic.
前記混合物がフッ素樹脂をさらに含むことが好ましい。
この構成によれば、摺動時にフッ素樹脂が時計用部品の表面に露出しやすくなり、耐摩耗性が向上する。
It is preferable that the mixture further contains a fluororesin.
With this configuration, the fluororesin is more likely to be exposed on the surface of the timepiece component during sliding, improving wear resistance.
前記混合物が無機粉末をさらに含むことが好ましい。
前記無機粉末を前記混合物中に等間隔に分散させることが好ましい。
この構成によれば、ゾルゲル反応領域を減らすことができるので成形時（ゾルの硬化時）の収縮量を低減でき、ヒケを抑制できる。特に、無機粉末を混合物中に等間隔に分散させれば、ブラッグの法則により光の特定波長が反射し、時計用部品が着色しているように見え、外観が向上する。
It is preferred that the mixture further comprises an inorganic powder.
It is preferred that the inorganic powder is dispersed evenly throughout the mixture.
This structure reduces the sol-gel reaction area, so the amount of shrinkage during molding (when the sol hardens) can be reduced, and sink marks can be suppressed. In particular, if the inorganic powder is dispersed at equal intervals in the mixture, specific wavelengths of light are reflected according to Bragg's law, making the watch parts appear colored, improving their appearance.
前記混合物が着色剤をさらに含むことが好ましい。
この構成によれば、時計用部品が着色するので、外観が向上する。
Preferably, the mixture further comprises a colorant.
According to this configuration, the timepiece component is colored, improving its appearance.
本発明の一態様によれば、軽量化および非磁性化が可能な時計用部品、ムーブメントおよび時計を提供できる。
本発明の一態様によれば、軽量化および非磁性化が可能な時計用部品を簡易に製造できる時計用部品の製造方法を提供できる。
According to one aspect of the present invention, it is possible to provide a timepiece component, movement, and timepiece that can be made lightweight and non-magnetic.
According to one aspect of the present invention, it is possible to provide a method for manufacturing a timepiece component that can easily produce a timepiece component that can be made lightweight and non-magnetic.
［時計用部品］
本発明の一態様の時計用部品は、無機元素（Ｍｅ）と酸素（Ｏ）とを含む無機高分子材からなる。時計用部品が前記無機高分子材からなることにより、軽量化および非磁性化が可能となる。加えて、プラスチック等の有機材料からなる時計用部品と比べて耐候性にも優れる。
なお、本発明において「高分子」とは、質量平均分子量が５０００以上であることを意味する。無機高分子材の質量平均分子量は１万以上が好ましく、１０万以上がより好ましい。
[Watch parts]
The timepiece part of one embodiment of the present invention is made of an inorganic polymer material containing an inorganic element (Me) and oxygen (O). By making the timepiece part out of the inorganic polymer material, it is possible to make the timepiece part lightweight and non-magnetic. In addition, it has better weather resistance than timepiece parts made of organic materials such as plastics.
In the present invention, the term "polymer" means a material having a mass average molecular weight of at least 5000. The mass average molecular weight of the inorganic polymer material is preferably at least 10,000, and more preferably at least 100,000.
無機高分子材における無機元素（Ｍｅ）と酸素（Ｏ）とのモル比（Ｍｅ：Ｏ）は１：２～２：１が好ましい。前記モル比が上記範囲内であれば、無機高分子材が適度な硬さとなる。よって、本発明の時計用部品をある程度の硬さが求められる部品、例えばがんぎ歯車部やアンクル体として最適に使用できる。 The molar ratio (Me:O) of inorganic element (Me) to oxygen (O) in the inorganic polymer material is preferably 1:2 to 2:1. If the molar ratio is within the above range, the inorganic polymer material will have an appropriate hardness. Therefore, the watch part of the present invention can be optimally used as a part that requires a certain degree of hardness, such as an escape wheel part or an anchor body.
無機高分子材における無機元素（Ｍｅ）としては、例えばケイ素（Ｓｉ）、アルミニウム（Ａｌ）、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）などが挙げられる。これらの中でも、無機高分子材が無色透明となる観点では、ケイ素、アルミニウムが好ましい。
無機高分子材が無色透明であれば、時計用部品を例えばミステリーウォッチ用の部品としても適用できる。
ここで、「無色透明」とは、無色であり、かつ可視光領域の光のうちの少なくとも一部の波長域の光に対して透過性を有することを意味する。
Examples of the inorganic element (Me) in the inorganic polymeric material include silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), etc. Among these, silicon and aluminum are preferred from the viewpoint of making the inorganic polymeric material colorless and transparent.
If the inorganic polymer material is colorless and transparent, the watch part can be used as a part for a mystery watch, for example.
Here, "colorless and transparent" means colorless and transparent to light in at least a part of the wavelength range of light in the visible light region.
無機高分子材は、アルキル基をさらに含んでいてもよい。
アルキル基としては、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、オクチル基などが挙げられる。
The inorganic polymer material may further include an alkyl group.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, and an octyl group.
無機高分子材としては、下記分子式（１）で表される構造単位（１）、下記分子式（２）で表される構造単位（２）、下記分子式（３）で表される構造単位（３）、下記分子式（４）で表される構造単位（４）および下記分子式（５）で表される構造単位（５）からなる群より選ばれる１種以上の構造単位からなる化合物が挙げられる。
－（ＭｅＯ２）－ ・・・（１）
－（Ｍｅ２Ｒ１
２Ｏ３）－ ・・・（２）
－（Ｍｅ４Ｒ２
６Ｒ３Ｏ４）－ ・・・（３）
－（ＭｅｎＲ４
（２ｎ－２）Ｒ５Ｏｎ）－ ・・・（４）
－（ＭｅＲ６
２Ｏ）－ ・・・（５）
Examples of the inorganic polymeric material include compounds comprising one or more structural units selected from the group consisting of a structural unit (1) represented by the following molecular formula (1), a structural unit (2) represented by the following molecular formula (2), a structural unit (3) represented by the following molecular formula (3), a structural unit (4) represented by the following molecular formula (4), and a structural unit (5) represented by the following molecular formula (5).
-(MeO 2 )-...(1)
-( Me2R12O3 ) -... ( 2 )
-(Me 4 R 2 6 R 3 O 4 ) - (3)
-(Me n R 4 (2n-2) R 5 O n )-...(4)
-(MeR 6 2 O)-...(5)
分子式（１）～（５）中、Ｍｅは無機元素であり、Ｏは酸素元素である。
分子式（２）中、Ｒ１は一価の炭化水素基である。分子式（２）において、２つのＲ１は同じであってもよいし、異なっていてもよい。
分子式（３）中、Ｒ２は一価の炭化水素基であり、Ｒ３は二価の連結基である。分子式（３）において、６つのＲ２は同じであってもよいし、異なっていてもよい。
分子式（４）中、Ｒ４は一価の炭化水素基であり、Ｒ５は二価の連結基である。ｎは２～１００の数である。分子式（４）において、（２ｎ－２）個のＲ４は同じであってもよいし、異なっていてもよい。
分子式（５）中、Ｒ６は一価の炭化水素基である。分子式（５）において、２つのＲ６は同じであってもよいし、異なっていてもよい。
In the molecular formulas (1) to (5), Me is an inorganic element, and O is an oxygen element.
In the molecular formula (2), R 1 is a monovalent hydrocarbon group. In the molecular formula (2), the two R 1 may be the same or different.
In the molecular formula (3), R2 is a monovalent hydrocarbon group, and R3 is a divalent linking group. In the molecular formula (3), the six R2 may be the same or different.
In molecular formula (4), R4 is a monovalent hydrocarbon group, and R5 is a divalent linking group. n is a number from 2 to 100. In molecular formula (4), the (2n-2) R4s may be the same or different.
In the molecular formula (5), R6 is a monovalent hydrocarbon group. In the molecular formula (5), the two R6 may be the same or different.
Ｒ１、Ｒ２、Ｒ４およびＲ６の炭化水素基としては、それぞれアルキル基、アリール基などが挙げられる。
アルキル基の炭素数は１～１８が好ましく、１～１４がより好ましく、１～１０がさらに好ましく、１～８が特に好ましい。
アリール基の炭素数は６～１０が好ましく、６～８がより好ましい。
Ｒ１、Ｒ２、Ｒ４およびＲ６の炭化水素基の炭素数が増えるほど、無機高分子材が柔らかくなり、割れにくくなる傾向にある。
The hydrocarbon groups of R 1 , R 2 , R 4 and R 6 each include an alkyl group, an aryl group and the like.
The alkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 14 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
The aryl group preferably has 6 to 10 carbon atoms, and more preferably has 6 to 8 carbon atoms.
As the number of carbon atoms in the hydrocarbon groups of R 1 , R 2 , R 4 and R 6 increases, the inorganic polymer material tends to become softer and less susceptible to cracking.
Ｒ３およびＲ５の連結基としては、それぞれ二価の炭化水素基などが挙げられる。
二価の炭化水素基としては、アルキレン基、アリーレン基などが挙げられる。
アルキレン基の炭素数は２～１８が好ましく、２～１４がより好ましく、２～１０がさらに好ましく、２～８が特に好ましい。
アリーレン基の炭素数は６～１０が好ましく、６～８がより好ましい。
The linking groups for R3 and R5 each include a divalent hydrocarbon group.
Examples of the divalent hydrocarbon group include an alkylene group and an arylene group.
The alkylene group preferably has 2 to 18 carbon atoms, more preferably 2 to 14 carbon atoms, further preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
The arylene group preferably has 6 to 10 carbon atoms, and more preferably has 6 to 8 carbon atoms.
無機高分子材は、構造単位（１）～（５）のうちのいずれか１つの構造単位のみからなる化合物でもよいし、構造単位（１）～（５）のうちの２つ以上の構造単位からなる化合物でもよい。また、無機高分子材は、構造単位（１）～（５）のうちの１つ以上の構造単位からなる化合物の混合物でもよい。 The inorganic polymeric material may be a compound consisting of only one of the structural units (1) to (5), or may be a compound consisting of two or more of the structural units (1) to (5). The inorganic polymeric material may also be a mixture of compounds consisting of one or more of the structural units (1) to (5).
無機高分子材は、フッ素樹脂をさらに含んでいてもよい。
無機高分子材がフッ素樹脂をさらに含んでいれば、摺動時にフッ素樹脂が時計用部品の表面に露出しやすくなり、耐摩耗性が向上する。
The inorganic polymer material may further contain a fluororesin.
If the inorganic polymer material further contains a fluororesin, the fluororesin becomes more likely to be exposed on the surface of the timepiece component during sliding, improving wear resistance.
フッ素樹脂としては、例えばテトラフルオロエチレン（ＴＦＥ）、ヘキサフルオロプロピレン（ＨＦＰ）、フッ化ビニリデン（ＶＤＦ）、フッ化ビニル、パーフルオロアルキルビニルエーテル等のフッ素系モノマーの単独重合体または共重合体、これらフッ素系モノマーとオレフィン類との共重合体などが挙げられる。これらの中でも、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニル（ＰＶＦ）、テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体（ＦＥＰ）が好ましい。
これらフッ素樹脂は、１種を単独で使用してもよいし、２種以上を併用してもよい。
Examples of fluororesins include homopolymers or copolymers of fluorine-based monomers such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), vinylidene fluoride (VDF), vinyl fluoride, and perfluoroalkyl vinyl ether, and copolymers of these fluorine-based monomers and olefins. Among these, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) are preferred.
These fluororesins may be used alone or in combination of two or more.
フッ素樹脂は粉末状でもよいし、液状でもよいが、均一に分散しやすい観点から粉末状が好ましい。
フッ素樹脂が粉末状の場合、フッ素樹脂の平均粒子径は０．１～１μｍが好ましく、０．２～０．３μｍがより好ましい。
The fluororesin may be in a powder form or a liquid form, but is preferably in a powder form from the viewpoint of facilitating uniform dispersion.
When the fluororesin is in powder form, the average particle size of the fluororesin is preferably 0.1 to 1 μm, and more preferably 0.2 to 0.3 μm.
フッ素樹脂の含有量は、無機高分子材の総質量に対して１～５０質量％が好ましく、２０～３０質量％がより好ましい。フッ素樹脂の含有量が上記下限値以上であれば、耐摩耗性がより向上する。フッ素樹脂の含有量が上記上限値以下であれば、硬化時の反応がスムーズに進み、フッ素樹脂が分散した状態の時計用部品が得られやすくなる。 The content of the fluororesin is preferably 1 to 50% by mass, more preferably 20 to 30% by mass, based on the total mass of the inorganic polymer material. If the content of the fluororesin is equal to or greater than the lower limit, the abrasion resistance is improved. If the content of the fluororesin is equal to or less than the upper limit, the curing reaction proceeds smoothly, making it easier to obtain watch parts in which the fluororesin is dispersed.
無機高分子材は、無機粉末をさらに含んでいてもよい。
詳しくは後述するが、時計用部品はゾルゲル法により製造できる。無機高分子材が無機粉末をさらに含んでいれば、ゾルゲル反応領域を減らすことができるので、成形時（ゾルの硬化時）の収縮量を低減できる。その結果、ヒケ、すなわち成形品の表面が収縮することで生じる凹みや窪みを抑制できる。
The inorganic polymer material may further include an inorganic powder.
As will be described in detail later, watch parts can be manufactured by the sol-gel method. If the inorganic polymer material further contains inorganic powder, the sol-gel reaction area can be reduced, so the amount of shrinkage during molding (when the sol hardens) can be reduced. As a result, sink marks, i.e. dents or depressions caused by shrinkage of the surface of the molded product, can be suppressed.
無機粉末は、無機高分子材中、すなわち時計用部品中で等間隔に分散していることが好ましい。
無機粉末が等間隔に分散していれば、ブラッグの法則により光の特定波長が反射し、時計用部品が着色しているように見え、外観が向上する。
ここで、「等間隔に分散している」とは、時計用部品を任意の断面で観察したときに、その断面上で無機粉末が等間隔に存在していることを意味する。
It is preferable that the inorganic powder is dispersed at equal intervals in the inorganic polymer material, i.e., in the watch component.
If the inorganic powder is evenly distributed, then Bragg's law causes certain wavelengths of light to be reflected, making the watch components appear colored and improving their appearance.
Here, "dispersed at equal intervals" means that when the watch component is observed in any cross section, the inorganic powder is present at equal intervals on that cross section.
無機粉末としては、例えばガラス粉末；アルミナ、マグネシア、カルシア、コーディエライト、シリカ、ムライト、ジルコン、ジルコニア、チタニア等のセラミック粉末；金、銀、銅、アルミニウム、ケイ素等の反磁性体等の金属粉末などが挙げられる。これらの中でも、ガラス粉末、セラミック粉末が好ましく、シリカがより好ましい。
これら無機粉末は、１種を単独で使用してもよいし、２種以上を併用してもよい。
Examples of inorganic powders include glass powders, ceramic powders such as alumina, magnesia, calcia, cordierite, silica, mullite, zircon, zirconia, titania, etc., and metal powders such as diamagnetic materials such as gold, silver, copper, aluminum, silicon, etc. Among these, glass powders and ceramic powders are preferred, and silica is more preferred.
These inorganic powders may be used alone or in combination of two or more kinds.
無機粉末は球状であってもよいし、他の形状であってもよいが、均一に分散しやすい観点から球状が好ましい。
無機粉末の平均粒子径は０．０１～２０μｍが好ましく、０．２～０．５μｍがより好ましい。
The inorganic powder may be spherical or may have another shape, but is preferably spherical from the viewpoint of easiness of uniform dispersion.
The average particle size of the inorganic powder is preferably from 0.01 to 20 μm, and more preferably from 0.2 to 0.5 μm.
成形時の収縮量の低減の観点では、無機粉末の含有量は、無機高分子材の総質量に対して１～５０質量％が好ましく、２０～３０質量％がより好ましい。無機粉末の含有量が上記下限値以上であれば、成形時の収縮量を充分に低減できる。無機粉末の含有量が上記上限値以下であれば、詳しくは後述するが混合物（Ｍ）が硬くなりにくく、混合物（Ｍ）を加熱して得られるゾルを成形型に容易に充填できる。
無機粉末を等間隔に分散させる観点では、無機粉末の含有量は、無機高分子材の総質量に対して０．１～５０質量％が好ましく、２０～４０質量％がより好ましい。無機粉末の含有量が上記下限値以上であれば、時計用部品の少なくとも一部に光の反射が認められ、着色による外観が向上する。無機粉末の含有量が上記上限値以下であれば、混合物（Ｍ）が硬くなりにくく、混合物（Ｍ）を加熱して得られるゾルを成形型に容易に充填できる。
From the viewpoint of reducing the amount of shrinkage during molding, the content of the inorganic powder is preferably 1 to 50% by mass, more preferably 20 to 30% by mass, based on the total mass of the inorganic polymer material. If the content of the inorganic powder is equal to or greater than the lower limit, the amount of shrinkage during molding can be sufficiently reduced. If the content of the inorganic powder is equal to or less than the upper limit, the mixture (M) is less likely to harden, as described in detail below, and the sol obtained by heating the mixture (M) can be easily filled into a mold.
From the viewpoint of dispersing the inorganic powder at equal intervals, the content of the inorganic powder is preferably 0.1 to 50 mass %, more preferably 20 to 40 mass %, based on the total mass of the inorganic polymer material. If the content of the inorganic powder is equal to or greater than the lower limit, light reflection is observed in at least a part of the watch part, improving the appearance due to coloring. If the content of the inorganic powder is equal to or less than the upper limit, the mixture (M) is unlikely to harden, and the sol obtained by heating the mixture (M) can be easily filled into a mold.
無機高分子材は、着色剤をさらに含んでいてもよい。
無機高分子材が着色剤さらに含んでいれば、時計用部品が着色するので、外観が向上する。着色剤の種類やその組み合わせに応じて、時計用部品を様々な色に着色できる。また、着色剤の含有量により、色合いを制御することもできる。
The inorganic polymeric material may further include a colorant.
If the inorganic polymer material further contains a colorant, the watch part is colored, improving its appearance. Depending on the type and combination of colorants, the watch part can be colored in various colors. In addition, the color tone can be controlled by the content of the colorant.
着色剤としては、上述した無機粉末以外の顔料や染料などが挙げられる。これら着色剤は、１種を単独で使用してもよいし、２種以上を併用してもよい。
顔料としては、例えば黄土、バリウム黄、紺青、カドミウムレッド、硫酸バリウム、弁柄、鉄黒、カーボンブラック等の無機顔料；銅フタロシアニンブルー、銅フタロシアニングリーン、アントラキノン、キナクリドン、インジゴイド、ベンジジンイエロー、ナフトールレッド等の有機顔料；亜鉛、カドミウム、カルシウム、アルミニウム、イットリウム等の金属の酸化物または硫化物等を主成分とし、これに微量のマンガン、銀、銅、鉛等の活性化剤を添加し、高温で焼成した無機蛍光顔料（具体的にはＣａＳ：Ｂｉ、ＣａＯ：Ｚｎ、ＺｎＳ：Ｃｕ、ＺｎＳ：Ｍｎ、ＺｎＳ：Ａｇ等）；アクリル樹脂、塩化ビニル樹脂等の樹脂マトリックス中に蛍光染料を固溶体化した有機蛍光顔料などが挙げられる。これらの中でも、無機蛍光顔料、有機蛍光顔料が好ましい。
これら顔料は、１種を単独で使用してもよいし、２種以上を併用してもよい。
The colorant may be a pigment or a dye other than the inorganic powders described above. These colorants may be used alone or in combination of two or more.
Examples of pigments include inorganic pigments such as yellow ochre, barium yellow, Prussian blue, cadmium red, barium sulfate, red iron oxide, iron black, and carbon black; organic pigments such as copper phthalocyanine blue, copper phthalocyanine green, anthraquinone, quinacridone, indigoid, benzidine yellow, and naphthol red; inorganic fluorescent pigments (specifically, CaS:Bi, CaO:Zn, ZnS:Cu, ZnS:Mn, ZnS:Ag, etc.) that are mainly composed of oxides or sulfides of metals such as zinc, cadmium, calcium, aluminum, and yttrium, to which trace amounts of activators such as manganese, silver, copper, and lead are added and baked at high temperatures; and organic fluorescent pigments in which a fluorescent dye is solid-dissolved in a resin matrix such as an acrylic resin or a vinyl chloride resin. Among these, inorganic fluorescent pigments and organic fluorescent pigments are preferred.
These pigments may be used alone or in combination of two or more kinds.
染料としては、カロチン、フラボン、フラボノール、カルコン、ナフトキノン、アントラキノン、タンニン、インジゴ、ベンゾビラン、カラメル色素、クチナシ色素、アントシアニン色素、アナトー色素、パプリカ色素、紅花色素、紅麹色素、フラボノイド色素、コチニール色素等の天然染料；アニリン黒、ナフトキノン染料、インジゴ染料、ニグロシン染料、フタロシアニン染料、ポリメチン染料、タール色素（例えばアマランス、エリスロシン、アルラレッドＡＣ、ニューコクシン、フロキシン、ローズベンガル、アシッドレッド、タートラジン、サンセットイエローＦＣＦ、ファストグリーンＦＣＦ、ブリリアントブルーＦＣＦ、インジゴカルミンなど）等の合成染料；メロシアニン、ペリレン、アクリジン、ルシフェリン、ピラニン、スチルベン、ローダミン、クマリン、ピロメテン、フルオレセイン、ウンベリフェロン等の蛍光染料などが挙げられる。これらの中でも、蛍光染料が好ましい。
これら染料は、１種を単独で使用してもよいし、２種以上を併用してもよい。
Examples of dyes include natural dyes such as carotene, flavone, flavonol, chalcone, naphthoquinone, anthraquinone, tannin, indigo, benzopyran, caramel color, gardenia color, anthocyanin color, annatto color, paprika color, safflower color, red yeast rice color, flavonoid color, and cochineal color; synthetic dyes such as aniline black, naphthoquinone dye, indigo dye, nigrosine dye, phthalocyanine dye, polymethine dye, and tar color (e.g., amaranth, erythrosine, allura red AC, new coccine, phloxine, rose bengal, acid red, tartrazine, sunset yellow FCF, fast green FCF, brilliant blue FCF, and indigo carmine); and fluorescent dyes such as merocyanine, perylene, acridine, luciferin, pyranine, stilbene, rhodamine, coumarin, pyrromethene, fluorescein, and umbelliferone. Among these, fluorescent dyes are preferred.
These dyes may be used alone or in combination of two or more.
着色剤の含有量は、無機高分子材の総質量に対して０．１～１００００質量ｐｐｍが好ましく、１００～３００質量ｐｐｍがより好ましい。着色剤の含有量が上記下限値以上であれば、着色による外観がより向上する。着色剤の含有量が上記上限値以下であれば、透明性が損なわれにくい。 The content of the colorant is preferably 0.1 to 10,000 ppm by mass, and more preferably 100 to 300 ppm by mass, relative to the total mass of the inorganic polymer material. If the content of the colorant is equal to or greater than the lower limit, the appearance due to coloring is further improved. If the content of the colorant is equal to or less than the upper limit, transparency is less likely to be impaired.
上述した無機高分子材からなる時計用部品の具体例としては、例えばがんぎ車を構成するがんぎ歯車部、アンクルを構成するアンクル体などが挙げられる。
図１に示すがんぎ歯車部１０は、環状のリム部１１と、リム部１１の内側に配置されたハブ部１２と、これらリム部１１およびハブ部１２を連結する複数のスポーク部１３とを有している。ハブ部１２は円板形状である。各スポーク部１３は、ハブ部１２の外周縁からリム部１１の内周縁に向かって放射状に延在している。リム部１１の外周面には、特殊な鉤型状に形成された複数の歯部１４が径方向の外側に向けて突設されている。
なお、がんぎ車は、がんぎ歯車部１０と、がんぎ歯車部１０に同軸で固定される軸部材（図示略）とを備えるものである。
Specific examples of timepiece parts made of the above-mentioned inorganic polymer material include an escape wheel portion that constitutes an escape wheel, and an pallet body that constitutes an pallet.
The
The escape wheel includes an
図２に示すアンクル体２０は、３つのアンクルビーム２１によってＴ字状に形成されている。
なお、アンクルは、アンクル体２０と、アンクル体２０に固定されるアンクル真（図示略）と、３つのアンクルビーム２１のうちの２つのアンクルビーム２１の先端に設けられる爪石（図示略）と、残り１つのアンクルビーム２１の先端に取り付けられるアンクルハコ（図示略）とを備えるものである。
The
The pallet comprises an
また、時計用部品は、例えば香箱車、二番車、三番車、四番車などの部品としても好適に使用できる。
時計用部品の厚さは特に制限されないが、軽量化の観点から１００～２００μｍが好ましい。
Furthermore, the timepiece parts can also be suitably used as parts such as a barrel, second wheel, third wheel, and fourth wheel.
There are no particular limitations on the thickness of the watch part, but from the standpoint of weight reduction, a thickness of 100 to 200 μm is preferable.
［時計用部品の製造方法］
時計用部品は、例えばゾルゲル法により製造できる。具体的には、無機元素（Ｍｅ）およびアルコキシ基を含む化合物（Ｘ）と、水と、触媒とを含む混合物（Ｍ）を加熱してゾルを得た後に、得られたゾルを加熱して所望の形状に硬化することで、ゾルの硬化物である無機高分子材からなる時計用部品を製造する。
混合物（Ｍ）は、必要に応じて、上述したフッ素樹脂、無機粉末および着色剤の１つ以上をさらに含んでいてもよい。
混合物（Ｍ）は、化合物（Ｘ）、水および触媒と、必要に応じてフッ素樹脂、無機粉末および着色剤の１つ以上とを混合することで得られる。各成分の混合には、スターラー、ミックスローター、ミキサー、超音波分散装置等の装置を用いればよい。特に、混合物（Ｍ）中に無機粉末等を等間隔に分散させるには、超音波分散装置を用いることが好ましい。超音波分散装置としてはホモジナイザーなどが挙げられる。
[Manufacturing method for watch parts]
The watch part can be manufactured by, for example, a sol-gel method. Specifically, a mixture (M) containing an inorganic element (Me) and an alkoxy group-containing compound (X), water, and a catalyst is heated to obtain a sol, and the obtained sol is then heated to harden into a desired shape, thereby manufacturing a watch part made of an inorganic polymer material that is a hardened product of the sol.
The mixture (M) may further contain one or more of the above-mentioned fluororesin, inorganic powder, and colorant, if necessary.
The mixture (M) is obtained by mixing the compound (X), water, a catalyst, and, if necessary, one or more of a fluororesin, an inorganic powder, and a colorant. A stirrer, a mix rotor, a mixer, an ultrasonic dispersion device, or the like may be used to mix the components. In particular, it is preferable to use an ultrasonic dispersion device to disperse the inorganic powder, etc., at equal intervals in the mixture (M). Examples of the ultrasonic dispersion device include a homogenizer.
化合物（Ｘ）は、無機高分子材の原料である。
化合物（Ｘ）としては、アルコキシシラン、アルミニウムアルコキシド、チタンアルコキシド、ジルコニウムアルコキシドなどが挙げられる。
アルコキシシランとしては、例えばトリメチルメトキシシラン、トリメチルエトキシシラン等のモノアルコキシシラン；ジメトキシジメチルシラン、ジメチルジエトキシシラン、ジエトキシメチルシラン、ジエトキシメチルビニルシラン等のジアルコキシシラン；メチルトリメトキシシラン、メチルトリエトキシシラン、オクチルトリエトキシシラン等のトリアルコキシシラン；テトラメトキシシラン、テトラエトキシシラン等のテトラアルコキシシランなどが挙げられる。
アルミニウムアルコキシドとしては、例えばアルミニウムエトキシドなどが挙げられる。
チタンアルコキシドとしては、例えばテトラエトキシチタンなどが挙げられる。
ジルコニウムアルコキシドとしては、例えばジルコニウムエトキシドなどが挙げられる。
これらの中でも、無機高分子材が無色透明な時計用部品が得られる観点では、アルコキシシラン、アルミニウムアルコキシドが好ましい。
これら化合物（Ｘ）は、１種を単独で使用してもよいし、２種以上を併用してもよい。
The compound (X) is a raw material for an inorganic polymer material.
Examples of the compound (X) include alkoxysilanes, aluminum alkoxides, titanium alkoxides, and zirconium alkoxides.
Examples of alkoxysilanes include monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; dialkoxysilanes such as dimethoxydimethylsilane, dimethyldiethoxysilane, diethoxymethylsilane and diethoxymethylvinylsilane; trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane and octyltriethoxysilane; and tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane.
The aluminum alkoxide includes, for example, aluminum ethoxide.
An example of the titanium alkoxide is tetraethoxytitanium.
An example of the zirconium alkoxide is zirconium ethoxide.
Among these, from the viewpoint of obtaining colorless and transparent watch parts from inorganic polymer materials, alkoxysilanes and aluminum alkoxides are preferred.
These compounds (X) may be used alone or in combination of two or more.
触媒としては、酢酸、塩酸、硝酸等の酸；水酸化ナトリウム、水酸化カリウム等のアルカリなどが挙げられる。
これら触媒は、１種を単独で使用してもよいし、２種以上を併用してもよい。
Examples of the catalyst include acids such as acetic acid, hydrochloric acid, and nitric acid; and alkalis such as sodium hydroxide and potassium hydroxide.
These catalysts may be used alone or in combination of two or more.
混合物（Ｍ）中の水の割合は、化合物（Ｘ）中のアルコキシ基の全てが加水分解できる量であれば特に制限されないが、例えば化合物（Ｘ）と水とのモル比（Ｘ：水）は、１０：５～１０：４０が好ましく、１０：１０～１０：２０がより好ましい。 The proportion of water in mixture (M) is not particularly limited as long as it is an amount that can hydrolyze all of the alkoxy groups in compound (X), but for example, the molar ratio of compound (X) to water (X:water) is preferably 10:5 to 10:40, and more preferably 10:10 to 10:20.
混合物（Ｍ）中の触媒の割合は、触媒量であれば特に制限されないが、例えば化合物（Ｘ）と触媒とのモル比（Ｘ：触媒）は、１０：０．１～１０：１０が好ましく、１０：１～１０：２がより好ましい。 The proportion of the catalyst in the mixture (M) is not particularly limited as long as it is a catalytic amount, but for example, the molar ratio of the compound (X) to the catalyst (X:catalyst) is preferably 10:0.1 to 10:10, and more preferably 10:1 to 10:2.
混合物（Ｍ）がフッ素樹脂を含む場合、混合物（Ｍ）中のフッ素樹脂の割合は、水および触媒を除いた混合物（Ｍ）の総質量に対して１～５０質量％が好ましく、２０～３０質量％がより好ましい。フッ素樹脂の含有量が上記下限値以上であれば、耐摩耗性がより向上する。フッ素樹脂の含有量が上記上限値以下であれば、硬化時の反応がスムーズに進み、フッ素樹脂が分散した状態の時計用部品が得られやすくなる。 When mixture (M) contains a fluororesin, the proportion of the fluororesin in mixture (M) is preferably 1 to 50 mass %, more preferably 20 to 30 mass %, based on the total mass of mixture (M) excluding water and catalyst. If the content of the fluororesin is equal to or greater than the above lower limit, the abrasion resistance is further improved. If the content of the fluororesin is equal to or less than the above upper limit, the curing reaction proceeds smoothly, making it easier to obtain watch parts in which the fluororesin is dispersed.
混合物（Ｍ）が無機粉末を含む場合、成形時の収縮量の低減の観点では、混合物（Ｍ）中の無機粉末の割合は、水および触媒を除いた混合物（Ｍ）の総質量に対して１～５０質量％が好ましく、２０～３０質量％がより好ましい。無機粉末の含有量が上記下限値以上であれば、成形時の収縮量を充分に低減できる。無機粉末の含有量が上記上限値以下であれば、混合物（Ｍ）が硬くなりにくく、混合物（Ｍ）を加熱して得られるゾルを成形型に容易に充填できる。
無機粉末を等間隔に分散させる観点では、混合物（Ｍ）中の無機粉末の割合は、水および触媒を除いた混合物（Ｍ）の総質量に対して０．１～５０質量％が好ましく、２０～４０質量％がより好ましい。無機粉末の含有量が上記下限値以上であれば、時計用部品の少なくとも一部に光の反射が認められ、着色による外観が向上する。無機粉末の含有量が上記上限値以下であれば、混合物（Ｍ）が硬くなりにくく、混合物（Ｍ）を加熱して得られるゾルを成形型に容易に充填できる。
When the mixture (M) contains an inorganic powder, the proportion of the inorganic powder in the mixture (M) is preferably 1 to 50 mass% and more preferably 20 to 30 mass% based on the total mass of the mixture (M) excluding water and catalyst, from the viewpoint of reducing the amount of shrinkage during molding. If the content of the inorganic powder is equal to or greater than the above lower limit, the amount of shrinkage during molding can be sufficiently reduced. If the content of the inorganic powder is equal to or less than the above upper limit, the mixture (M) is less likely to harden, and the sol obtained by heating the mixture (M) can be easily filled into a mold.
From the viewpoint of dispersing the inorganic powder at equal intervals, the ratio of the inorganic powder in the mixture (M) is preferably 0.1 to 50 mass %, more preferably 20 to 40 mass %, based on the total mass of the mixture (M) excluding water and the catalyst. If the content of the inorganic powder is equal to or greater than the lower limit, light reflection is observed in at least a part of the watch part, improving the appearance due to coloring. If the content of the inorganic powder is equal to or less than the upper limit, the mixture (M) is less likely to harden, and the sol obtained by heating the mixture (M) can be easily filled into a mold.
混合物（Ｍ）が着色剤を含む場合、混合物（Ｍ）中の着色剤の割合は、水および触媒を除いた混合物（Ｍ）の総質量に対して０．１～１００００質量ｐｐｍが好ましく、１００～３００質量ｐｐｍがより好ましい。着色剤の含有量が上記下限値以上であれば、着色による外観がより向上する。着色剤の含有量が上記上限値以下であれば、透明性が損なわれにくい。 When mixture (M) contains a colorant, the proportion of the colorant in mixture (M) is preferably 0.1 to 10,000 ppm by mass, and more preferably 100 to 300 ppm by mass, based on the total mass of mixture (M) excluding water and catalyst. If the content of the colorant is equal to or greater than the above lower limit, the appearance due to coloring is further improved. If the content of the colorant is equal to or less than the above upper limit, transparency is less likely to be impaired.
混合物（Ｍ）の加熱は、化合物（Ｘ）中のアルコキシ基の全てが加水分解するまでの間は、水の蒸発を防ぐ目的で、密閉系で行われることが好ましい。化合物（Ｘ）中のアルコキシ基が加水分解されると、アルコールが生成する。このアルコールは、硬化時のクラックの原因となることがあるため、硬化前に除去しておくことが好ましい。よって、密閉系での加熱（第一の加熱工程）の後に、開放系にてさらに加熱処理（第二の加熱工程）することが好ましい。
第一の加熱工程において、加熱温度は５０～１００℃が好ましく、加熱時間は３０分～２４時間が好ましい。
第二の加熱工程において、加熱温度は８０～１２０℃が好ましく、加熱時間は１～２４時間が好ましい。
The mixture (M) is preferably heated in a closed system until all of the alkoxy groups in the compound (X) are hydrolyzed in order to prevent water from evaporating. When the alkoxy groups in the compound (X) are hydrolyzed, alcohol is generated. This alcohol may cause cracks during curing, so it is preferable to remove it before curing. Therefore, it is preferable to further heat the mixture (second heating step) in an open system after heating in a closed system (first heating step).
In the first heating step, the heating temperature is preferably 50 to 100° C., and the heating time is preferably 30 minutes to 24 hours.
In the second heating step, the heating temperature is preferably 80 to 120° C., and the heating time is preferably 1 to 24 hours.
混合物（Ｍ）を加熱することで化合物（Ｘ）中のアルコキシ基の全てが加水分解し、ゾルが得られる。
得られたゾルの質量平均分子量は５０００以上が好ましく、１万以上がより好ましく、１０万以上がさらに好ましい。
ゾルの質量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によって測定される標準ポリスチレン換算の値である。
なお、ゾルの硬化物である無機高分子材の質量平均分子量は、硬化前のゾルの質量平均分子量よりも大きい。よって、硬化前のゾルの質量平均分子量が５０００以上であれば、無機高分子材の質量平均分子量も５０００以上であるとみなす。
By heating the mixture (M), all of the alkoxy groups in the compound (X) are hydrolyzed to obtain a sol.
The mass average molecular weight of the obtained sol is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 100,000 or more.
The mass average molecular weight of the sol is a value calculated as a standard polystyrene equivalent, measured by gel permeation chromatography (GPC).
The mass average molecular weight of the inorganic polymer material, which is the cured product of the sol, is greater than the mass average molecular weight of the sol before curing. Therefore, if the mass average molecular weight of the sol before curing is 5000 or more, the mass average molecular weight of the inorganic polymer material is also considered to be 5000 or more.
得られたゾルは例えば任意の成形型に充填される。
成形型としては、時計用部品の用途に応じた型を用いればよい。
成形型は、例えば以下のようにして製造できる。
まず、シリコンウェハ等の基板上に蒸着法やスパッタ法により金属の皮膜を形成した後、皮膜上にレジストを塗布し、乾燥させてレジスト層を形成する。レジスト層の厚さは時計用部品（例えば、がんぎ歯車部やアンクル体等）の厚さと同等とする。
次いで、レジスト層に対して紫外線等を所望のパターン状に照射してレジスト層を露光する。レジスト層を露光すると、紫外線の照射によりレジスト層が硬化した領域（硬化部）と、紫外線が照射されずにレジスト層が硬化しない領域（非硬化部）とが形成される。
次いで、レジスト層を現像し、レジスト層の非硬化部を除去することで成形型が得られる。
The obtained sol is filled, for example, into any mold.
The molding die used may be one suited to the intended use of the watch part.
The mold can be produced, for example, as follows.
First, a metal film is formed on a substrate such as a silicon wafer by vapor deposition or sputtering, and then a resist is applied to the film and dried to form a resist layer. The thickness of the resist layer is set to be equal to the thickness of the timepiece component (e.g., escape wheel portion, pallet fork, etc.).
Next, the resist layer is exposed to ultraviolet light or the like in a desired pattern. When the resist layer is exposed, regions in which the resist layer is hardened by the ultraviolet light irradiation (hardened portions) and regions in which the resist layer is not hardened because it is not irradiated with ultraviolet light (non-hardened portions) are formed.
The resist layer is then developed and the uncured parts of the resist layer are removed to obtain the mold.
ゾルを成形型に充填する際には、必要に応じて硬化促進剤をゾルに添加してもよい。
硬化促進剤としては、ジブチル錫ジアセテート、Ｋａｒｓｔｅｄｔ触媒などが挙げられる。
ゾルと硬化促進剤とのモル比（ゾル：硬化促進剤）は、１０：０．０１～１０：１が好ましく、１０：０．１～１０：０．２がより好ましい。
When the sol is filled into the mold, a curing accelerator may be added to the sol, if necessary.
The curing accelerator includes dibutyltin diacetate, Karstedt's catalyst, and the like.
The molar ratio of the sol to the curing accelerator (sol:curing accelerator) is preferably from 10:0.01 to 10:1, and more preferably from 10:0.1 to 10:0.2.
また、上述したフッ素樹脂、無機粉末および着色剤の１つ以上を、混合物（Ｍ）に配合せずに、ゾルに添加してもよい。
フッ素樹脂の添加量は、得られる無機高分子材の総質量に対するフッ素樹脂の含有量が上述した範囲内となる量が好ましい。
無機粉末の添加量は、得られる無機高分子材の総質量に対する無機粉末の含有量が上述した範囲内となる量が好ましい。
着色剤の添加量は、得られる無機高分子材の総質量に対する着色剤の含有量が上述した範囲内となる量が好ましい。
Moreover, one or more of the above-mentioned fluororesin, inorganic powder and colorant may be added to the sol without being blended in the mixture (M).
The amount of the fluororesin added is preferably an amount such that the content of the fluororesin relative to the total mass of the resulting inorganic polymer material falls within the above-mentioned range.
The amount of inorganic powder added is preferably an amount such that the content of the inorganic powder relative to the total mass of the resulting inorganic polymer material falls within the above-mentioned range.
The amount of the colorant added is preferably an amount such that the content of the colorant relative to the total mass of the resulting inorganic polymer material falls within the above-mentioned range.
成形型に充填したゾルを加熱して硬化することでゾルがゲル化する。
次いで、成形型からゾルの硬化物を取り出して、ゾルの硬化物である無機高分子材からなる時計用部品が得られる。
ゾルの加熱温度は１００～２００℃が好ましく、加熱時間は３０分～４８時間が好ましい。
成形型からゾルの硬化物を取り出す方法は特に限定されず、例えばレジスト層の硬化部を除去した後、皮膜を除去すればよい。
The sol filled in the mold is heated and cured to gel.
Next, the cured sol is removed from the mold, yielding a watch part made of an inorganic polymer material, which is a cured sol.
The heating temperature of the sol is preferably 100 to 200° C., and the heating time is preferably 30 minutes to 48 hours.
There are no particular limitations on the method for removing the cured sol from the mold. For example, the cured portion of the resist layer may be removed, and then the coating may be removed.
化合物（Ｘ）として、例えばジアルコキシシランを用いた場合、前記構造単位（３）、前記構造単位（４）および前記構造単位（５）の少なくとも一方を有する無機高分子材が得られる。
化合物（Ｘ）として、例えばトリアルコキシシランを用いた場合、前記構造単位（２）を有する無機高分子材が得られる。
化合物（Ｘ）として、例えばテトラアルコキシシランを用いた場合、前記構造単位（１）を有する無機高分子材が得られる。
When, for example, a dialkoxysilane is used as the compound (X), an inorganic polymer material having at least one of the structural unit (3), the structural unit (4) and the structural unit (5) can be obtained.
When, for example, a trialkoxysilane is used as the compound (X), an inorganic polymer material having the structural unit (2) is obtained.
When, for example, tetraalkoxysilane is used as the compound (X), an inorganic polymer material having the structural unit (1) is obtained.
ゾルの硬化物である無機高分子材は、シリコンに比べて靭性に優れる。よって、上述した時計用部品の製造方法によれば、無機高分子材の表面を合金膜、または酸化膜と合金膜との積層膜で被覆する必要がないので、軽量化および非磁性化が可能な時計用部品を簡易に製造できる。 The inorganic polymer material, which is the hardened product of the sol, has superior toughness compared to silicon. Therefore, according to the above-mentioned manufacturing method for watch parts, it is not necessary to cover the surface of the inorganic polymer material with an alloy film or a laminated film of an oxide film and an alloy film, so that watch parts that can be made lightweight and non-magnetic can be easily manufactured.
なお、上述した時計用部品の製造方法では、ゲルを成形型に充填して硬化させているが、例えばゲルを板状に硬化した後に、切削、研削等の機械加工などにより所望の形状にゲルの硬化物を加工して、時計用部品を製造してもよい。
また、ゾルを射出成型して時計用部品を製造してもよい。
また、上述した成形型ではパターン形成にレジストを用いているが、例えば歯車を製造する場合にはレジスト層の代わりに歯形形状の金属箔を基板上に積層してもよい。
In the manufacturing method for watch parts described above, the gel is filled into a mold and hardened, but the watch part may also be manufactured by, for example, hardening the gel into a plate shape and then processing the hardened gel into the desired shape by machining such as cutting and grinding.
The sol may also be injection molded to produce watch parts.
Furthermore, in the above-mentioned mold, a resist is used for pattern formation, but when manufacturing a gear, for example, a metal foil having a tooth shape may be laminated on a substrate instead of a resist layer.
また、インサート成形により時計用部品を製造してもよい。例えば時計用部品が歯車である場合は、歯車の中心にかなを取り付けるが、歯車用の成形型の中心部に金属製のリングを配置してゾルを充填し、硬化させれば、中心部にリングが取り付けられた無機高分子材からなる歯車を一体成形できる。歯車にリングが取り付けられていることで、このリングにかなを打ち込むことができる。また、歯車用の成形型の中心部にかなを配置してゾルを充填し、硬化させてもよい。これにより、中心部にかなが取り付けられた無機高分子材からなる歯車を一体成形できる。
なお、インサート成形により得られた時計用部品を「インサート成形品」ともいう。
Also, watch parts may be manufactured by insert molding. For example, if the watch part is a gear, a pinion is attached to the center of the gear, but if a metal ring is placed in the center of the gear mold, and sol is filled and cured, a gear made of inorganic polymer material with a ring attached to the center can be molded as a single piece. By attaching the ring to the gear, the pinion can be driven into the ring. Also, a pinion may be placed in the center of the gear mold, and sol is filled and cured. This allows a gear made of inorganic polymer material with a pinion attached to the center to be molded as a single piece.
In addition, watch parts obtained by insert molding are also called "insert molded products."
［ムーブメント、時計］
一般に、時計の駆動部分を含む機械体を「ムーブメント」と称する。
本発明の一態様のムーブメントは、本発明の時計用部品を備える。すなわち、ムーブメントを構成する部品の少なくとも一部が本発明の時計用部品からなる。具体的には、がんぎ歯車部、アンクル体、香箱車、二番車、三番車、四番車などの１つ以上が、本発明の時計用部品からなることが好ましい。残りのムーブメントを構成する部品については特に限定されず、公知のものを使用できる。
本発明の一態様の時計は、本発明のムーブメントを備え、具体的には、ムーブメントや文字板、各種指針等が時計ケース内に組み込まれて構成される。
これらムーブメントおよび時計は、本発明の時計用部品を備えているので、軽量である。
[Movement, Clock]
Generally, the mechanical body including the moving parts of a watch is called the "movement."
A movement according to one embodiment of the present invention is equipped with the timepiece component of the present invention. That is, at least a portion of the components constituting the movement are made of the timepiece component of the present invention. Specifically, it is preferable that one or more of the escape wheel portion, anchor body, barrel, center wheel, third wheel, fourth wheel, etc. are made of the timepiece component of the present invention. There are no particular limitations on the remaining components constituting the movement, and known components can be used.
A timepiece according to one aspect of the present invention comprises the movement of the present invention, and specifically, the movement, dial, various hands, etc. are assembled in a timepiece case.
These movements and watches are equipped with the timepiece parts of the invention and are therefore lightweight.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to these.
［成形型の作製］
シリコンウェハの表面にスタッパ法により銅膜を形成した後、乾燥後の膜厚が１２０μｍとなるように銅膜上にレジストを塗布し、乾燥させてレジスト層を形成した。
次いで、図１に示すがんぎ歯車部１０の形状となるように、紫外線をレジスト層に対してパターン状に照射してレジスト層を露光した。
次いで、レジスト層を現像し、レジスト層の非硬化部を除去することで成形型を得た。
[Preparation of mold]
A copper film was formed on the surface of a silicon wafer by a stepper method, and then a resist was applied onto the copper film so that the film thickness after drying would be 120 μm, and then dried to form a resist layer.
Next, the resist layer was exposed to ultraviolet light in a pattern so as to have the shape of the
Next, the resist layer was developed and the uncured parts of the resist layer were removed to obtain a molding die.
［評価］
がんぎ歯車部の硬さについて、がんぎ車に適した硬さの場合を「Ａ」を評価し、がんぎ車には適さない硬さ（柔らかすぎる）場合を「Ｂ」と評価した。
[evaluation]
Regarding the hardness of the escape wheel part, when the hardness was suitable for an escape wheel, it was rated as "A", and when the hardness was not suitable for an escape wheel (too soft), it was rated as "B".
［実施例１］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例１で得られた無機高分子材は、前記構造単位（１）に相当する－（ＳｉＯ２）－からなる。
[Example 1]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1:water:acetic acid) of 10:15:1, and the resulting mixture was stirred in a closed system at 78°C for 30 minutes (first heating step), and then stirred in an open system at 100°C for 1 hour (second heating step) to obtain a sol. After the first heating step was completed, it was confirmed that separation of water due to hydrolysis had ceased. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 1 is composed of --(SiO 2 )--, which corresponds to the structural unit (1).
［実施例２］
テトラエトキシシラン（Ｘ－１）と、メチルトリエトキシシラン（Ｘ－２）と、水と、酢酸とをモル比（Ｘ－１：Ｘ－２：水：酢酸）で５：５：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例２で得られた無機高分子材は、前記構造単位（１）に相当する－（ＳｉＯ２）－からなる化合物と、前記構造単位（２）に相当する－（Ｓｉ２（ＣＨ３）２Ｏ３）－からなる化合物の混合物である。－（Ｓｉ２（ＣＨ３）２Ｏ３）－は、具体的には下記式（２－１）で表される。
[Example 2]
Tetraethoxysilane (X-1), methyltriethoxysilane (X-2), water, and acetic acid were mixed in a molar ratio (X-1:X-2:water:acetic acid) of 5:5:15:1, and the resulting mixture was stirred at 78°C in a closed system for 30 minutes (first heating step), and then stirred at 100°C in an open system for 1 hour (second heating step) to obtain a sol. After the first heating step was completed, it was confirmed that separation of water due to hydrolysis had ceased. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 2 was a mixture of a compound consisting of -(SiO 2 )-, which corresponds to the structural unit (1), and a compound consisting of -(Si 2 (CH 3 ) 2 O 3 )-, which corresponds to the structural unit (2). -(Si 2 (CH 3 ) 2 O 3 )- is specifically represented by the following formula (2-1).
［実施例３］
メチルトリエトキシシラン（Ｘ－２）と、水と、酢酸とをモル比（Ｘ－２：水：酢酸）で１０：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例３で得られた無機高分子材は、前記構造単位（２）に相当する－（Ｓｉ２（ＣＨ３）２Ｏ３）－からなる。－（Ｓｉ２（ＣＨ３）２Ｏ３）－は、具体的には前記式（２－１）で表される。
[Example 3]
Methyltriethoxysilane (X-2), water, and acetic acid were mixed in a molar ratio (X-2: water: acetic acid) of 10:15:1, and the resulting mixture was stirred in a closed system at 78°C for 30 minutes (first heating step), and then stirred in an open system at 100°C for 1 hour (second heating step) to obtain a sol. After the first heating step was completed, it was confirmed that separation of water due to hydrolysis had ceased. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 3 is composed of -(Si 2 (CH 3 ) 2 O 3 )-, which corresponds to the structural unit (2). -(Si 2 (CH 3 ) 2 O 3 )- is specifically represented by the formula (2-1) above.
［実施例４］
オクチルトリエトキシシラン（Ｘ－３）と、水と、酢酸とをモル比（Ｘ－３：水：酢酸）で１０：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で１５時間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルとジブチル錫ジアセテートとをモル比（ゾル：ジブチル錫ジアセテート）で１０：０．１となるように混合し、得られた混合物を成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例４で得られた無機高分子材は、前記構造単位（２）に相当する－（Ｓｉ２（Ｃ８Ｈ１７）２Ｏ３）－からなる。－（Ｓｉ２（Ｃ８Ｈ１７）２Ｏ３）－は、具体的には下記式（２－２）で表される。
[Example 4]
Octyltriethoxysilane (X-3), water, and acetic acid were mixed in a molar ratio (X-3:water:acetic acid) of 10:15:1, and the resulting mixture was stirred in a closed system at 78°C for 15 hours (first heating step), and then stirred in an open system at 100°C for 1 hour (second heating step) to obtain a sol. After the first heating step was completed, it was confirmed that separation of water due to hydrolysis had ceased. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
Next, the obtained sol was mixed with dibutyltin diacetate in a molar ratio (sol:dibutyltin diacetate) of 10:0.1, and the obtained mixture was filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 4 is composed of -(Si 2 (C 8 H 17 ) 2 O 3 )-, which corresponds to the structural unit (2). -(Si 2 (C 8 H 17 ) 2 O 3 )- is specifically represented by the following formula (2-2).
［実施例５］
メチルトリエトキシシラン（Ｘ－２）と、ジメチルジエトキシシラン（Ｘ－４）と、水と、酢酸とをモル比（Ｘ－２：Ｘ－３：水：酢酸）で５：５：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例５で得られた無機高分子材は、前記構造単位（２）に相当する－（Ｓｉ２（ＣＨ３）２Ｏ３）－からなる化合物と、前記構造単位（５）に相当する－（Ｓｉ（ＣＨ３）２Ｏ）－からなる化合物の混合物である。－（Ｓｉ２（ＣＨ３）２Ｏ３）－は、具体的には前記式（２－１）で表され、－（Ｓｉ（ＣＨ３）２Ｏ）－は、具体的には下記式（２－３）で表される。
[Example 5]
Methyltriethoxysilane (X-2), dimethyldiethoxysilane (X-4), water, and acetic acid were mixed in a molar ratio (X-2:X-3:water:acetic acid) of 5:5:15:1, and the resulting mixture was stirred at 78°C for 30 minutes in a closed system (first heating step), and then stirred at 100°C for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water by hydrolysis had ceased after the first heating step. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 5 was a mixture of a compound consisting of -(Si 2 (CH 3 ) 2 O 3 )-, which corresponds to the structural unit (2), and a compound consisting of -(Si(CH 3 ) 2 O)-, which corresponds to the structural unit (5). -(Si 2 (CH 3 ) 2 O 3 )- is specifically represented by the above formula (2-1), and -(Si(CH 3 ) 2 O)- is specifically represented by the following formula (2-3).
［実施例６］
ジメチルジエトキシシラン（Ｘ－４）と、ジエトキシメチルビニルシラン（Ｘ－５）と、ジエトキシメチルシラン（Ｘ－６）と、水と、酢酸とをモル比（Ｘ－４：Ｘ－５：Ｘ－６：水：酢酸）で５：２．５：２．５：１０：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例６で得られた無機高分子材は、前記構造単位（３）に相当する－（Ｓｉ４（ＣＨ３）６Ｃ２Ｈ４Ｏ４）－からなる。－（Ｓｉ４（ＣＨ３）６Ｃ２Ｈ４Ｏ４）－は、具体的には下記式（２－４）で表される。
[Example 6]
Dimethyldiethoxysilane (X-4), diethoxymethylvinylsilane (X-5), diethoxymethylsilane (X-6), water, and acetic acid were mixed in a molar ratio (X-4:X-5:X-6:water:acetic acid) of 5:2.5:2.5:10:1, and the resulting mixture was stirred at 78°C for 30 minutes in a closed system (first heating step), and then stirred at 100°C for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water by hydrolysis had ceased after the first heating step. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 6 is composed of -(Si 4 (CH 3 ) 6 C 2 H 4 O 4 )-, which corresponds to the structural unit (3). -(Si 4 (CH 3 ) 6 C 2 H 4 O 4 )- is specifically represented by the following formula (2-4).
［実施例７］
ジメチルジエトキシシラン（Ｘ－４）と、トリメチルエトキシシラン（Ｘ－７）と、水と、酢酸とをモル比（Ｘ－２：Ｘ－３：水：酢酸）で５：５：１５：１となるように混合し、得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、このゾルは分子量が５０００以上の化合物を含むものであった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部の硬さを評価した。結果を表１に示す。
なお、実施例７で得られた無機高分子材は、具体的には下記式（２－５）で表される化合物が複数種類混在した混合物の状態で得られた。式（２－５）中、ｍは０～１００の数である。
[Example 7]
Dimethyldiethoxysilane (X-4), trimethylethoxysilane (X-7), water, and acetic acid were mixed in a molar ratio (X-2:X-3:water:acetic acid) of 5:5:15:1, and the resulting mixture was stirred at 78°C for 30 minutes in a closed system (first heating step), and then stirred at 100°C for 1 hour in an open system (second heating step) to obtain a sol. After the first heating step was completed, it was confirmed that separation of water due to hydrolysis had ceased. In addition, when the mass average molecular weight of the obtained sol was measured, this sol contained a compound having a molecular weight of 5000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The hardness of the obtained escape wheel portion was evaluated, and the results are shown in Table 1.
The inorganic polymer material obtained in Example 7 was specifically obtained in the form of a mixture of multiple types of compounds represented by the following formula (2-5): In formula (2-5), m is a number from 0 to 100.
各実施例で得られたがんぎ歯車部にかなを配置し、ムーブメントに組み込んで時計を作製した。こうして得られた時計は、金属製のがんぎ歯車部を備えた時計と同等の精度で動作した。しかも、各実施例で得られたがんぎ歯車部は無機高分子材からなるので、非磁性であるとともに、金属製のがんぎ歯車部に比べて軽量であった。
このように、各実施例によれば、軽量化および非磁性化が可能ながんぎ歯車部を簡易に製造できた。特に無機高分子材におけるＳｉとＯとのモル比（Ｓｉ：Ｏ）が１：２～１：１である実施例１～６で得られたがんぎ歯車部は、がんぎ車に適した硬さを有していた。
A pinion was placed on the escape wheel portion obtained in each example and assembled into a movement to produce a watch. The watch thus obtained operated with the same accuracy as a watch equipped with a metal escape wheel portion. Moreover, since the escape wheel portion obtained in each example was made of an inorganic polymer material, it was non-magnetic and lighter than a metal escape wheel portion.
In this way, according to each example, it was possible to easily manufacture an escape wheel portion that could be made lightweight and non-magnetic. In particular, the escape wheel portions obtained in Examples 1 to 6, in which the molar ratio of Si to O (Si:O) in the inorganic polymer material was 1:2 to 1:1, had hardness suitable for an escape wheel.
［実施例８］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらにフッ素樹脂として平均粒子径が０．２～０．３μｍであるＰＴＦＥ粒子（テクノケミカル株式会社製、商品名「ＤｉｓｐｅｒｓＥＺ」）を、テトラエトキシシラン（Ｘ－１）およびＰＴＦＥ粒子の総質量に対するＰＴＦＥ粒子の割合が２５質量％となるに添加し、ホモジナイザーで３時間超音波分散して混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部について、ボールオンディスク法に基づき摩擦摩耗試験を行ったところ、実施例１で得られたがんぎ歯車部に比べて摩耗量を約５０％削減できた。
[Example 8]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, PTFE particles (manufactured by Techno Chemical Co., Ltd., product name "DispersEZ") having an average particle size of 0.2 to 0.3 μm as a fluororesin were added so that the ratio of PTFE particles to the total mass of tetraethoxysilane (X-1) and PTFE particles was 25% by mass, and ultrasonically dispersed with a homogenizer for 3 hours to obtain a mixture. The obtained mixture was stirred at 78 ° C. for 30 minutes in a closed system (first heating step), and then stirred at 100 ° C. for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water by hydrolysis had ceased after the end of the first heating step. In addition, the mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
A friction and wear test was conducted on the obtained escape gear portion based on the ball-on-disk method, and the amount of wear was reduced by approximately 50% compared to the escape gear portion obtained in Example 1.
［実施例９］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらに無機粉末として平均粒子径が０．３μｍであるシリカ球状微粒子（株式会社日本触媒製、商品名「ＫＥ－Ｐ３０」）を、テトラエトキシシラン（Ｘ－１）およびシリカ球状微粒子の総質量に対するシリカ球状微粒子の割合が２０質量％となるに添加し、混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部は、成形時（ゾルの硬化時）の収縮量を低減でき、実施例１で得られたがんぎ歯車部に比べてヒケを抑制できた。
[Example 9]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, silica spherical particles having an average particle size of 0.3 μm (manufactured by Nippon Shokubai Co., Ltd., product name "KE-P30") were added as inorganic powder so that the ratio of the silica spherical particles to the total mass of tetraethoxysilane (X-1) and the silica spherical particles was 20 mass% to obtain a mixture. The obtained mixture was stirred at 78° C. for 30 minutes in a closed system (first heating step), and then stirred at 100° C. for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water due to hydrolysis had ceased after the first heating step. The mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The obtained escape wheel portion was able to reduce the amount of shrinkage during molding (when the sol hardened), and sink marks were suppressed compared to the escape wheel portion obtained in Example 1.
［実施例１０］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらに無機粉末として平均粒子径が０．２μｍであるシリカ球状微粒子（株式会社日本触媒製、商品名「ＫＥ－Ｐ２０」）を、テトラエトキシシラン（Ｘ－１）およびシリカ球状微粒子の総質量に対するシリカ球状微粒子の割合が３５質量％となるに添加し、ホモジナイザーで３時間超音波分散して混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部は、反射時は青色に見え、透過時は赤色に見えた。
[Example 10]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, silica spherical particles having an average particle size of 0.2 μm (manufactured by Nippon Shokubai Co., Ltd., product name "KE-P20") were added as inorganic powder so that the ratio of silica spherical particles to the total mass of tetraethoxysilane (X-1) and silica spherical particles was 35 mass%, and ultrasonically dispersed with a homogenizer for 3 hours to obtain a mixture. The obtained mixture was stirred at 78° C. for 30 minutes in a closed system (first heating step), and then stirred at 100° C. for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water due to hydrolysis had ceased after the end of the first heating step. In addition, the mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The resulting escape wheel portion appeared blue in reflected light and red in transmitted light.
［実施例１１］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらに顔料としてローダミンＢ（東京化成工業株式会社製、商品名「Ｒ００４０」）を、テトラエトキシシラン（Ｘ－１）およびローダミンＢの総質量に対するローダミンＢの割合が１００質量ｐｐｍとなるに添加し、ホモジナイザーで３時間超音波分散して混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部は、赤色に着色していた。
[Example 11]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., product name "R0040") was added as a pigment so that the ratio of rhodamine B to the total mass of tetraethoxysilane (X-1) and rhodamine B was 100 mass ppm, and ultrasonically dispersed with a homogenizer for 3 hours to obtain a mixture. The obtained mixture was stirred at 78 ° C. for 30 minutes in a closed system (first heating step), and then stirred at 100 ° C. for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water due to hydrolysis had ceased after the end of the first heating step. In addition, the mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The resulting escape wheel portion was colored red.
［実施例１２］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらに顔料としてフルオレセイン（東京化成工業株式会社製、商品名「Ｆ００９５」）を、テトラエトキシシラン（Ｘ－１）およびフルオレセインの総質量に対するフルオレセインの割合が１００質量ｐｐｍとなるに添加し、ホモジナイザーで３時間超音波分散して混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部は、黄色に着色しており、紫外線を照射すると照射部が緑色に発光した。
[Example 12]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, fluorescein (manufactured by Tokyo Chemical Industry Co., Ltd., product name "F0095") was added as a pigment so that the ratio of fluorescein to the total mass of tetraethoxysilane (X-1) and fluorescein was 100 mass ppm, and ultrasonically dispersed with a homogenizer for 3 hours to obtain a mixture. The obtained mixture was stirred at 78°C for 30 minutes in a closed system (first heating step), and then stirred at 100°C for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water due to hydrolysis had ceased after the end of the first heating step. In addition, the mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
The obtained escape wheel portion was colored yellow, and when irradiated with ultraviolet light, the irradiated portion emitted green light.
［実施例１３］
テトラエトキシシラン（Ｘ－１）と、水と、酢酸とをモル比（Ｘ－１：水：酢酸）で１０：１５：１となるように混合した。さらに顔料としてウンベリフェロン（東京化成工業株式会社製、商品名「Ｈ０２３６」）を、テトラエトキシシラン（Ｘ－１）およびフルオレセインの総質量に対するフルオレセインの割合が１００質量ｐｐｍとなるに添加し、ホモジナイザーで３時間超音波分散して混合物を得た。得られた混合物を密閉系にて７８℃で３０分間撹拌した後（第一の加熱工程）、開放系にて１００℃で１時間撹拌し（第二の加熱工程）、ゾルを得た。なお、第一の加熱工程の終了後、加水分解により水の分離がなくなったことを確認した。また、得られたゾルの質量平均分子量を測定したところ、１０万以上であった。
次いで、得られたゾルを成形型に充填し、１５０℃で３０分間加熱してゾルを架橋、硬化させた。
次いで、レジスト層の硬化部を除去した後、銅膜を除去して、ゾルの硬化物である無機高分子材からなるがんぎ歯車部を得た。
得られたがんぎ歯車部は、紫外線を照射すると照射部が青色に発光した。
[Example 13]
Tetraethoxysilane (X-1), water, and acetic acid were mixed in a molar ratio (X-1: water: acetic acid) of 10:15:1. Furthermore, umbelliferone (manufactured by Tokyo Chemical Industry Co., Ltd., product name "H0236") was added as a pigment so that the ratio of fluorescein to the total mass of tetraethoxysilane (X-1) and fluorescein was 100 mass ppm, and ultrasonically dispersed with a homogenizer for 3 hours to obtain a mixture. The obtained mixture was stirred at 78°C for 30 minutes in a closed system (first heating step), and then stirred at 100°C for 1 hour in an open system (second heating step) to obtain a sol. It was confirmed that separation of water due to hydrolysis had ceased after the end of the first heating step. In addition, the mass average molecular weight of the obtained sol was measured and found to be 100,000 or more.
The resulting sol was then filled into a mold and heated at 150° C. for 30 minutes to crosslink and harden the sol.
Next, the hardened portion of the resist layer was removed, and then the copper film was removed to obtain an escape gear portion made of an inorganic polymer material, which is a hardened product of the sol.
When the obtained escape wheel portion was irradiated with ultraviolet light, the irradiated portion emitted a blue light.
１０ がんぎ歯車部
１１ リム部
１２ ハブ部
１３ スポーク部
１４ 歯部
２０ アンクル体
２１ アンクルビーム
REFERENCE SIGNS
Claims (16)
無機元素（Ｍｅ）と酸素（Ｏ）とを含む無機高分子材からなる、時計用部品。 A timepiece component which is at least one selected from an escape wheel portion, an anchor body, a barrel, a center wheel, a third wheel, and a fourth wheel, and has a thickness of 100 to 200 μm,
A watch component made of an inorganic polymer material containing an inorganic element (Me) and oxygen (O).
無機元素（Ｍｅ）およびアルコキシ基を含む化合物と、水と、触媒とを含む混合物を加熱してゾルを得た後に、得られたゾルを加熱して硬化する、時計用部品の製造方法。 A method for manufacturing a timepiece part which is at least one selected from an escape wheel portion, an anchor body, a barrel, a center wheel, a third wheel, and a fourth wheel and has a thickness of 100 to 200 μm, comprising the steps of:
A method for manufacturing a watch part, comprising heating a mixture containing an inorganic element (Me) and an alkoxy group-containing compound, water, and a catalyst to obtain a sol, and then heating the obtained sol to harden it .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH000262/2021A CH717221B1 (en) | 2020-03-11 | 2021-03-11 | Component of a timepiece, manufacturing process, movement and timepiece |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020041663 | 2020-03-11 | ||
| JP2020041663 | 2020-03-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021144024A JP2021144024A (en) | 2021-09-24 |
| JP7545871B2 true JP7545871B2 (en) | 2024-09-05 |
Family
ID=77766395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020196739A Active JP7545871B2 (en) | 2020-03-11 | 2020-11-27 | Watch components and their manufacturing method, movement and watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7545871B2 (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001112517A (en) | 1999-10-21 | 2001-04-24 | Arii Gosei Kogyosho:Kk | Method for producing wrist watch band |
| JP2001240846A (en) | 2000-02-29 | 2001-09-04 | Citizen Watch Co Ltd | Rubber packing, outer case member, and wrist watch |
| JP2003096301A (en) | 2001-09-25 | 2003-04-03 | Shin Etsu Chem Co Ltd | Silicone rubber composition for sealing electric / electronic parts |
| JP2007010888A (en) | 2005-06-29 | 2007-01-18 | Seiko Epson Corp | Liquid crystal device, method for manufacturing liquid crystal device, and electronic apparatus |
| JP2007275548A (en) | 2005-11-17 | 2007-10-25 | Seiko Epson Corp | Fluid transport device |
| JP2017193604A (en) | 2016-04-18 | 2017-10-26 | 株式会社トウペ | Silicone resin composition and coated article |
| JP2018025699A (en) | 2016-08-10 | 2018-02-15 | セイコーエプソン株式会社 | Electrophoretic display device and electronic apparatus |
| CN211207078U (en) | 2019-12-31 | 2020-08-07 | 杭州手表有限公司 | Full-transparent tourbillon watch |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10301497A (en) * | 1997-04-22 | 1998-11-13 | Kawaguchiko Seimitsu Kk | Display board and its manufacture |
-
2020
- 2020-11-27 JP JP2020196739A patent/JP7545871B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001112517A (en) | 1999-10-21 | 2001-04-24 | Arii Gosei Kogyosho:Kk | Method for producing wrist watch band |
| JP2001240846A (en) | 2000-02-29 | 2001-09-04 | Citizen Watch Co Ltd | Rubber packing, outer case member, and wrist watch |
| JP2003096301A (en) | 2001-09-25 | 2003-04-03 | Shin Etsu Chem Co Ltd | Silicone rubber composition for sealing electric / electronic parts |
| JP2007010888A (en) | 2005-06-29 | 2007-01-18 | Seiko Epson Corp | Liquid crystal device, method for manufacturing liquid crystal device, and electronic apparatus |
| JP2007275548A (en) | 2005-11-17 | 2007-10-25 | Seiko Epson Corp | Fluid transport device |
| JP2017193604A (en) | 2016-04-18 | 2017-10-26 | 株式会社トウペ | Silicone resin composition and coated article |
| JP2018025699A (en) | 2016-08-10 | 2018-02-15 | セイコーエプソン株式会社 | Electrophoretic display device and electronic apparatus |
| CN211207078U (en) | 2019-12-31 | 2020-08-07 | 杭州手表有限公司 | Full-transparent tourbillon watch |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021144024A (en) | 2021-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5319293B2 (en) | Transparent or translucent glass ceramic plate and method for producing the same | |
| JP6724898B2 (en) | Light-scattering complex forming composition, light-scattering complex and method for producing the same | |
| JP5221122B2 (en) | Silicone resin base material | |
| CN110128688A (en) | A kind of radiation refrigeration film and preparation method thereof | |
| EP3068192A1 (en) | Heating cooker | |
| CN1137220C (en) | Multilayer coated powder | |
| CN104244862A (en) | Dental products and procedures | |
| JPH02212337A (en) | Three-layered irreflexive coating composition and preparation thereof | |
| EP2099835A2 (en) | Polymers with transmission into the ultraviolet | |
| JP7545871B2 (en) | Watch components and their manufacturing method, movement and watch | |
| JP2018107472A (en) | Optical semiconductor light-emitting device, lighting appliance, display device, and method for manufacturing optical semiconductor light-emitting device | |
| CN1104474C (en) | colorant composition | |
| FR2862635A1 (en) | Transparent glass/vitroceramic plates coated with a colored opaque coating able to withstand high temperatures for cooker applications | |
| CN1124920C (en) | Article having uneven surface and method for manufacturing same | |
| JP2022145953A (en) | Enhanced wavelength conversion device | |
| TWI742708B (en) | Color conversion panel | |
| CN107429050A (en) | The product of absorbance with reduction | |
| JP6287747B2 (en) | Light-scattering composition, light-scattering composite, and method for producing the same | |
| JP5722368B2 (en) | Silicone resin base material | |
| JP6047674B2 (en) | Reflective composition | |
| JP2015028188A (en) | Silicone resin base material | |
| CN101213084B (en) | method for furnishing utensils with decoration | |
| CH717221B1 (en) | Component of a timepiece, manufacturing process, movement and timepiece | |
| JP7296932B2 (en) | optically enhanced light transducer | |
| WO2014152824A1 (en) | Polyheterosiloxane composition and silicone composition including a polyheterosiloxane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230906 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240228 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240305 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240416 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240604 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240703 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20240806 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20240826 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7545871 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |