JP7371890B2 - Components and methods of manufacturing components - Google Patents
Components and methods of manufacturing components Download PDFInfo
- Publication number
- JP7371890B2 JP7371890B2 JP2019169340A JP2019169340A JP7371890B2 JP 7371890 B2 JP7371890 B2 JP 7371890B2 JP 2019169340 A JP2019169340 A JP 2019169340A JP 2019169340 A JP2019169340 A JP 2019169340A JP 7371890 B2 JP7371890 B2 JP 7371890B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- polymerizable
- member according
- compound
- 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 12
- 238000000034 method Methods 0.000 title description 33
- 150000001875 compounds Chemical class 0.000 claims description 98
- 239000000203 mixture Substances 0.000 claims description 52
- 238000002844 melting Methods 0.000 claims description 41
- 230000008018 melting Effects 0.000 claims description 41
- 229920000642 polymer Polymers 0.000 claims description 34
- 125000005647 linker group Chemical group 0.000 claims description 15
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- -1 poly(ε-caprolactone) Polymers 0.000 description 26
- 230000000694 effects Effects 0.000 description 16
- 150000001923 cyclic compounds Chemical class 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 description 13
- 230000007087 memory ability Effects 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 8
- VVLRVPJYFLFSQG-UHFFFAOYSA-N 6-tridecyloxan-2-one Chemical compound CCCCCCCCCCCCCC1CCCC(=O)O1 VVLRVPJYFLFSQG-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- JDBCCUBGERLOBZ-UHFFFAOYSA-N epsilon-palmitolactone Natural products CCCCCCCCCCC1CCCCC(=O)O1 JDBCCUBGERLOBZ-UHFFFAOYSA-N 0.000 description 8
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 8
- 230000002902 bimodal effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- IPBFYZQJXZJBFQ-UHFFFAOYSA-N gamma-octalactone Chemical compound CCCCC1CCC(=O)O1 IPBFYZQJXZJBFQ-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920001610 polycaprolactone Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- QTWLQDVFHKLZRA-UHFFFAOYSA-N 4-ethyloxetan-2-one Chemical compound CCC1CC(=O)O1 QTWLQDVFHKLZRA-UHFFFAOYSA-N 0.000 description 4
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 4
- VNXMFQWTDCWMDQ-UHFFFAOYSA-N 5-methyloxepan-2-one Chemical compound CC1CCOC(=O)CC1 VNXMFQWTDCWMDQ-UHFFFAOYSA-N 0.000 description 4
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 4
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229960000380 propiolactone Drugs 0.000 description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 3
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-UHFFFAOYSA-N 0.000 description 3
- AZFRDTPVZYJHGZ-UHFFFAOYSA-N 7-ethyloxepan-2-one Chemical compound CCC1CCCCC(=O)O1 AZFRDTPVZYJHGZ-UHFFFAOYSA-N 0.000 description 3
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical group CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical group OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 239000005541 ACE inhibitor Substances 0.000 description 1
- 229940127291 Calcium channel antagonist Drugs 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical group OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical group OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229940122029 DNA synthesis inhibitor Drugs 0.000 description 1
- 229940121710 HMGCoA reductase inhibitor Drugs 0.000 description 1
- 102000014150 Interferons Human genes 0.000 description 1
- 108010050904 Interferons Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000002333 angiotensin II receptor antagonist Substances 0.000 description 1
- 229940044094 angiotensin-converting-enzyme inhibitor Drugs 0.000 description 1
- 239000005557 antagonist Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000000043 antiallergic agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003524 antilipemic agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229940127218 antiplatelet drug Drugs 0.000 description 1
- 239000003435 antirheumatic agent Substances 0.000 description 1
- 229940127217 antithrombotic drug Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VWPUAXALDFFXJW-UHFFFAOYSA-N benzenehexol Chemical compound OC1=C(O)C(O)=C(O)C(O)=C1O VWPUAXALDFFXJW-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- FZKPWSBMFSLEFL-UHFFFAOYSA-N butane-1,1-diol;butane-1,4-diol Chemical compound CCCC(O)O.OCCCCO FZKPWSBMFSLEFL-UHFFFAOYSA-N 0.000 description 1
- 239000000480 calcium channel blocker Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- RUOFFXZEQYHVHT-UHFFFAOYSA-N cyclohexane-1,1,2,2,3-pentol Chemical group OC1CCCC(O)(O)C1(O)O RUOFFXZEQYHVHT-UHFFFAOYSA-N 0.000 description 1
- FNTHQRXVZDCWSP-UHFFFAOYSA-N cyclohexane-1,1,2-triol Chemical group OC1CCCCC1(O)O FNTHQRXVZDCWSP-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 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
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000003102 growth factor Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- KDPXOGYCOOUWOS-UHFFFAOYSA-N hexyl 2-hydroxypropanoate Chemical compound CCCCCCOC(=O)C(C)O KDPXOGYCOOUWOS-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002471 hydroxymethylglutaryl coenzyme A reductase inhibitor Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229960003444 immunosuppressant agent Drugs 0.000 description 1
- 239000003018 immunosuppressive agent Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N inositol Chemical group OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 229940125798 integrin inhibitor Drugs 0.000 description 1
- 229940047124 interferons Drugs 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 210000002464 muscle smooth vascular Anatomy 0.000 description 1
- 239000002840 nitric oxide donor Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002444 phloroglucinyl group Chemical group [H]OC1=C([H])C(O[H])=C(*)C(O[H])=C1[H] 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229940096701 plain lipid modifying drug hmg coa reductase inhibitors Drugs 0.000 description 1
- 239000000106 platelet aggregation inhibitor Substances 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004492 retinoid derivatives Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PYKSLEHEVAWOTJ-UHFFFAOYSA-N tetrabutoxystannane Chemical compound CCCCO[Sn](OCCCC)(OCCCC)OCCCC PYKSLEHEVAWOTJ-UHFFFAOYSA-N 0.000 description 1
- FPADWGFFPCNGDD-UHFFFAOYSA-N tetraethoxystannane Chemical compound [Sn+4].CC[O-].CC[O-].CC[O-].CC[O-] FPADWGFFPCNGDD-UHFFFAOYSA-N 0.000 description 1
- TWRYZRQZQIBEIE-UHFFFAOYSA-N tetramethoxystannane Chemical compound [Sn+4].[O-]C.[O-]C.[O-]C.[O-]C TWRYZRQZQIBEIE-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical group C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SSWCPXKXMAZRJO-UHFFFAOYSA-J tri(tetradecanoyloxy)stannyl tetradecanoate Chemical compound [Sn+4].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O SSWCPXKXMAZRJO-UHFFFAOYSA-J 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229940121358 tyrosine kinase inhibitor Drugs 0.000 description 1
- 239000005483 tyrosine kinase inhibitor Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、部材、及び、部材の製造方法に関する。 The present invention relates to a member and a method for manufacturing the member.
ポリカプロラクトン等の脂肪族ポリエステル樹脂は優れた生分解性を有することが知られており、研究が進められている。非特許文献１には、温度応答性ポリ（εカプロラクトン）フィルムが記載されている。 Aliphatic polyester resins such as polycaprolactone are known to have excellent biodegradability, and research is underway. Non-Patent Document 1 describes a temperature-responsive poly(ε-caprolactone) film.
非特許文献１に記載されたフィルムは、変形を受けた後の「Ｔｅｍｐｏｒａｒｙ」形状と、予め記憶された「Ｐｅｒｍａｎｅｎｔ」形状との間の形状変化が外部からの熱的刺激により惹起されるという優れた特徴を有していた。言い換えれば、上記フィルムは２段階の形状記憶能を有していた。 The film described in Non-Patent Document 1 has the advantage that the shape change between the "Temporary" shape after deformation and the "Permanent" shape stored in advance is induced by external thermal stimulation. It had certain characteristics. In other words, the film had two levels of shape memory ability.
しかし、本発明者らは、上記形状記憶能は「Ｔｅｍｐｏｒａｒｙ」形状と、「Ｐｅｒｍａｎｅｎｔ」形状の２段階の形状を記憶できる機能であり、記憶できる形状の数にさらなる改善の余地があることを知見した。 However, the present inventors found that the above shape memory ability is a function that can memorize two levels of shapes: "Temporary" shape and "Permanent" shape, and that there is room for further improvement in the number of shapes that can be memorized. did.
そこで、本発明は、外部からの熱的刺激により３段階以上の形状変化が惹起される機能（以下「３段階以上の形状記憶能」ともいう。）を有する部材を提供することを課題とする。また、本発明は部材の製造方法を提供することも課題とする。 Therefore, an object of the present invention is to provide a member having a function of causing shape change in three or more stages (hereinafter also referred to as "shape memory ability in three or more stages") by external thermal stimulation. . Another object of the present invention is to provide a method for manufacturing a member.
本発明者らは、上記課題を達成すべく鋭意検討した結果、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by the following configuration.
［１］ 後述する式１で表される重合性化合物を含有する組成物を硬化させてなる結晶性を有する硬化物と、オキシアルキレンカルボニル基からなる繰り返し単位を有し、結晶性を有する高分子化合物とを含有する部材。
［２］ 示差走査熱量測定を用いて観測される融解ピークが多峰性である、［１］に記載の部材。
［３］ 上記組成物が、上記式１中ｑが２である第１重合性化合物と、上記式１中ｑが３以上である第２重合性化合物とを含有する、［１］又は［２］に記載の部材。
［４］ 前記第２重合性化合物のｑが４である、［３］に記載の部材。
［５］ 上記組成物中における上記第１重合性化合物の含有量と上記第２重合性化合物の含有量の合計に対する、上記第２重合性化合物の含有量の含有モル比が０．２以上である、［３］又は［４］に記載の部材。
［６］ 上記融解ピークのうち、最も低温側のピーク温度が４０℃以下である、［２］に記載の部材。
［７］ 上記融解ピークのうち、最も高温側のピーク温度が６０℃以下である、［２］に記載の部材。
［８］ 上記重合性基がエチレン性不飽和基である、［１］～［７］のいずれかに記載の部材。
［９］ 上記重合性基を有する基が、後述する式３で表される基である［１］～［８］のいずれかに記載の部材。
［１０］ 上記ポリオキシアルキレンカルボニル基が、後述する式２で表される基である、［１］～［９］のいずれかに記載の部材。
［１１］ 上記ｎが、５～５０である、［１０］に記載の部材。
［１２］ 上記高分子化合物が、後述する式５で表される繰り返し単位を有する、［１０］又は［１１］に記載の部材。
［１３］ 上記Ｌ２と上記Ｌ５が同一の基である、［１２］に記載の部材。
［１４］ 後述する式１で表される重合性化合物を含有する組成物と、オキシアルキレンカルボニル基からなる繰り返し単位を有する高分子化合物と、を混合して混合物を得て、上記混合物にエネルギーを付与して上記組成物を硬化させ、［１］～［１３］のいずれかに記載の部材を得る、部材の製造方法。
[1] A crystalline cured product obtained by curing a composition containing a polymerizable compound represented by formula 1 described below, and a crystalline polymer having a repeating unit consisting of an oxyalkylene carbonyl group. A member containing a compound.
[2] The member according to [1], wherein the melting peak observed using differential scanning calorimetry is multimodal.
[3] [1] or [2], wherein the composition contains a first polymerizable compound in which q is 2 in the above formula 1 and a second polymerizable compound in which q in the above formula 1 is 3 or more. ] The member described in.
[4] The member according to [3], wherein q of the second polymerizable compound is 4.
[5] The molar ratio of the content of the second polymerizable compound to the sum of the content of the first polymerizable compound and the content of the second polymerizable compound in the composition is 0.2 or more. The member according to [3] or [4].
[6] The member according to [2], wherein the peak temperature at the lowest temperature among the melting peaks is 40°C or less.
[7] The member according to [2], wherein the peak temperature on the highest temperature side among the melting peaks is 60°C or less.
[8] The member according to any one of [1] to [7], wherein the polymerizable group is an ethylenically unsaturated group.
[9] The member according to any one of [1] to [8], wherein the group having a polymerizable group is a group represented by formula 3 described below.
[10] The member according to any one of [1] to [9], wherein the polyoxyalkylenecarbonyl group is a group represented by formula 2 described below.
[11] The member according to [10], wherein n is 5 to 50.
[12] The member according to [10] or [11], wherein the polymer compound has a repeating unit represented by formula 5 described below.
[13] The member according to [12], wherein L 2 and L 5 are the same group.
[14] A composition containing a polymerizable compound represented by formula 1 described below and a polymer compound having a repeating unit consisting of an oxyalkylene carbonyl group are mixed to obtain a mixture, and energy is applied to the mixture. A method for manufacturing a member, comprising applying the composition and curing the composition to obtain the member according to any one of [1] to [13].
本発明によれば、３段階以上の形状記憶能を有する（以下「本発明の効果を有する」ともいう。）部材を提供できる。また、本発明によれば、部材の製造方法も提供できる。 According to the present invention, it is possible to provide a member having three or more levels of shape memory ability (hereinafter also referred to as "having the effects of the present invention"). Further, according to the present invention, a method for manufacturing a member can also be provided.
以下、本発明について詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に制限されるものではない。
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
本明細書における基（原子群）の表記において、置換及び無置換を記していない表記は、本発明の効果を損ねない範囲で、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。このことは、各化合物についても同義である。
また、本明細書において、「（メタ）アクリレート」はアクリレート及びメタクリレートの双方、又は、いずれかを表し、「（メタ）アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表す。また、「（メタ）アクリロイル」はアクリロイル及びメタクリロイルの双方、又は、いずれかを表す。
In the description of groups (atomic groups) in this specification, descriptions that do not indicate substituted or unsubstituted include those without a substituent as well as those with a substituent to the extent that the effects of the present invention are not impaired. It is something to do. For example, the term "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). This also applies to each compound.
Moreover, in this specification, "(meth)acrylate" represents both or either of acrylate and methacrylate, and "(meth)acrylic" represents both or either of acrylic and methacrylic. Moreover, "(meth)acryloyl" represents both or either acryloyl and methacryloyl.
［部材］
本発明の実施形態に係る部材（以下「本部材」ともいう。）は、後述する式１で表される重合性化合物を含有する組成物を硬化させてなる結晶性を有する硬化物（以下、「特定硬化物」ともいう。）と、オキシアルキレンカルボニル基からなる繰り返し単位を有し、結晶性を有する高分子化合物（以下「特定高分子化合物」ともいう。）とを含有する部材である。
[Element]
A member according to an embodiment of the present invention (hereinafter also referred to as "this member") is a cured product having crystallinity (hereinafter referred to as "main member") obtained by curing a composition containing a polymerizable compound represented by formula 1 described below It is a member containing a crystalline polymer compound (hereinafter also referred to as a "specific polymer compound") that has a repeating unit consisting of an oxyalkylene carbonyl group (also referred to as a "specific cured product").
上記特徴を有する本部材が本発明の効果を有する機序としては必ずしも明らかではないが、本発明者らは以下のとおり推測している。なお、以下の機序は推測であり、以下の機序によらずに本発明の課題が解決される場合であっても、本発明の範囲に含まれるものとする。 Although the mechanism by which this member having the above characteristics has the effects of the present invention is not necessarily clear, the present inventors speculate as follows. Note that the following mechanisms are speculations, and even if the problem of the present invention is solved without relying on the following mechanisms, the scope of the present invention shall still fall within the scope of the present invention.
本部材が有する３段階以上の形状記能について図を用いて説明する。
本部材は特定硬化物と特定高分子化合物とを含有するため、示差走査熱量測定（ＤＳＣ）を用いて昇温測定すると、結晶の融解に係る吸熱ピーク（以下、単に「融解ピーク」ともいう。）が観察される。図１は、後述する部材１のＤＳＣ測定結果を模式的に表したものであり、実線が昇温過程（図中「ｈｅａｔｉｎｇ」と記載した。）、一点鎖線が冷却過程（図中「ｃｏｏｌｉｎｇ」と記載した。）を示している。なお、図１において、縦軸は負の方向（下方向）に吸熱（Ｅｎｄｏｔｈｅｒｍ）量を示している。横軸は、温度を示している。
The three or more levels of shape ability that this member has will be explained with reference to the drawings.
Since this member contains a specific cured product and a specific polymer compound, when measured at elevated temperature using differential scanning calorimetry (DSC), an endothermic peak (hereinafter also simply referred to as "melting peak") associated with crystal melting is observed. ) is observed. FIG. 1 schematically represents the DSC measurement results of member 1, which will be described later. The solid line represents the temperature increase process (denoted as "heating" in the diagram), and the dashed line represents the cooling process (described as "cooling" in the diagram). ). In FIG. 1, the vertical axis indicates the amount of endotherm in the negative direction (downward). The horizontal axis indicates temperature.
図１において、「ｈｅａｔｉｎｇ」と示した曲線（昇温過程）には低温側の結晶融解ピークのピーク温度Ｔ＿ｔｒａｎｓ１と、高温側の結晶融解ピークのピーク温度Ｔ＿ｔｒａｎｓ２とが存在し、部材の融解ピークが二峰性であることを示している。このような曲線は、例えば、特定硬化物の結晶の融解ピークと特定高分子化合物の結晶の融解ピークのピーク温度がそれぞれ異なること、特定硬化物、及び／又は、特定高分子化合物の結晶の融解ピークのピーク温度が２つ以上あること（例えば、部材が異なる種類の特定硬化物を含有する場合等）によって得られる。 In FIG. 1, the curve labeled "heating" (temperature raising process) has a peak temperature T_trans1 of the crystal melting peak on the low temperature side and a peak temperature T_trans2 of the crystal melting peak on the high temperature side, and the melting peak of the member is It shows that it is bimodal. Such a curve is based on, for example, the fact that the peak temperatures of the melting peak of the crystals of the specific cured product and the melting peak of the crystals of the specific polymer compound are different, the specific cured product and/or the melting of the crystals of the specific polymer compound. This is obtained by having two or more peak temperatures (for example, when the member contains different types of specific cured products).
なお、図１において、部材の結晶の融解ピークは二峰性であるが、本部材の融解ピークとしては上記に制限されず、例えば、特定硬化物の融解ピークと特定高分子化合物の融解ピークとが合成されて１つのブロードなピークに見えるものであってもよい。融解ピークが二峰性であると、形状を記憶させる際の温度設定がより明確な（言い換えれば、形状をより簡便に記憶させやすい）点で優れている。 In FIG. 1, the melting peak of the crystal of the member is bimodal, but the melting peak of the member is not limited to the above, and for example, the melting peak of a specific cured product and the melting peak of a specific polymer compound. may be combined to appear as one broad peak. A bimodal melting peak is advantageous in that the temperature setting when memorizing the shape can be more clearly defined (in other words, the shape can be more easily memorized).
また、本部材は、３つ以上の融解ピークを有していてもよい。その場合、融解ピークは低温側から順に、Ｔ＿ｔｒａｎｓ１、Ｔ＿ｔｒａｎｓ２、・・・、Ｔ＿ｔｒａｎｓＸ（但しＸは３以上の整数）と表すものとし、以下でも適宜、上記記号を用いて説明する。 Further, the present member may have three or more melting peaks. In that case, the melting peaks will be expressed as T_trans1, T_trans2, .
なお、融解ピークが多峰性であるとは、示差走査熱量分析計を用いて、昇温速度１０℃／分の速度で０～１２０℃まで昇温した後、５℃／分の速度で－２０℃まで冷却し、その後５℃／分の昇温速度で昇温した際の融解熱量曲線の極小値（融解ピーク）が２以上存在することを意味する。
また、融解ピークのピーク温度とは、融解熱量曲線（ＤＳＣ昇温過程の熱量曲線）のピークトップの温度を意味する。
Note that the melting peak is multimodal when the temperature is increased from 0 to 120°C at a rate of 10°C/min using a differential scanning calorimeter, and then at a rate of 5°C/min. This means that there are two or more minimum values (melting peaks) in the heat of fusion curve when the material is cooled to 20° C. and then heated at a temperature increase rate of 5° C./min.
Moreover, the peak temperature of the melting peak means the temperature at the top of the peak of the heat of fusion curve (the heat curve of the DSC heating process).
また、図１の「ｃｏｏｌｉｎｇ」と示した曲線（冷却過程）によれば、部材は、低温側と高温側とにそれぞれ２つの結晶化温度（発熱ピークのピーク温度）を有している。本部材としては上記に制限されず、例えば、特定硬化物の結晶化の発熱ピークと、特定高分子化合物の結晶化の発熱ピークとが合成されて１つのブロードなピークに見えるものであってもよい。 Further, according to the curve (cooling process) shown as "cooling" in FIG. 1, the member has two crystallization temperatures (peak temperatures of exothermic peaks) on the low temperature side and the high temperature side, respectively. This member is not limited to the above, and for example, even if the exothermic peak of crystallization of a specific cured product and the exothermic peak of crystallization of a specific polymer compound are synthesized and appear to be one broad peak. good.
次に、図２は、本部材の３段階の形状記憶能を説明するための模式図である。部材１００は外部からの熱的刺激により３段階に形状を変化させ得る、３段階の形状記憶能を有する。 Next, FIG. 2 is a schematic diagram for explaining three stages of shape memory ability of this member. The member 100 has a three-stage shape memory ability that can change its shape in three stages by external thermal stimulation.
当初、部材１００は平滑な表面形状（形状Ａ：第１段階）を有する平板状である。まず、部材１００に形状Ｂ（第２段階）を記憶させる。部材１００に形状Ｂを記憶させる方法としては、特に制限されないが、図１で説明したＴ＿ｔｒａｎｓ２以上の温度に部材１００を加熱し、形状Ｂへと変形させることが好ましい。部材１００は、すでに説明したとおり融解ピークが二峰性であるため、より高温側のＴ＿ｔｒａｎｓ２以上の温度に加熱して形状Ｂへと変形させることが好ましいが、３つ以上の融解ピークを有する場合（多峰性）、最も高温側の融解ピークの温度Ｔ＿ｔｒａｎｓＸ以上の温度に加熱すればよいし、融解ピークがブロードである場合は、特定硬化物と特定高分子化合物のそれぞれを単独でＤＳＣ測定したときに得られる最も高温側の融解ピークの温度をＴ＿ｔｒａｎｓＸとして、上記と同様の操作を行えばよい。 Initially, the member 100 has a flat plate shape with a smooth surface shape (shape A: first stage). First, the shape B (second stage) is stored in the member 100. The method for memorizing the shape B in the member 100 is not particularly limited, but it is preferable to heat the member 100 to a temperature equal to or higher than T_trans2 described in FIG. 1 to transform it into the shape B. As described above, the member 100 has bimodal melting peaks, so it is preferable to heat it to a temperature higher than T_trans2 on the higher temperature side and transform it into shape B. However, in the case where the member 100 has three or more melting peaks. (multimodal), it is sufficient to heat to a temperature equal to or higher than the temperature of the melting peak on the highest temperature side T_trans The same operation as above may be performed by setting the temperature of the melting peak on the highest temperature side that is sometimes obtained as T_transX.
Ｔ＿ｔｒａｎｓ２以上の温度に加熱した形状Ａの部材１００に外力を与えて加工する（例えばエンボス加工する）ことで形状Ｂへと変形することができる。部材の変形方法としては上記に制限されず、用途に応じて公知の変形方法を適宜選択すればよい。
部材１００は所定の温度で変形された後、外力を与えたまま、結晶化温度程度（例えば、図１中における「Ｔ＿ｃｒｙ」、典型的には結晶化温度未満）に冷却され、形状が固定される。形状が固定された後は外力を除いても、元の形状Ａには戻らず、これにより、形状Ｂの部材１０１が得られる（形状Ｂが記憶される。）。
By applying an external force to the member 100 having the shape A heated to a temperature of T_trans2 or higher and processing it (for example, by embossing it), it can be deformed into the shape B. The method of deforming the member is not limited to the above, and any known deformation method may be appropriately selected depending on the application.
After the member 100 is deformed at a predetermined temperature, it is cooled to about the crystallization temperature (for example, "T_cry" in FIG. 1, typically below the crystallization temperature) while applying an external force, and the shape is fixed. Ru. After the shape is fixed, even if an external force is removed, the member 101 does not return to the original shape A, and thus the member 101 having shape B is obtained (shape B is memorized).
このとき、冷却温度はＴ＿ｃｒｙ程度であればよいが、図１のようにＤＳＣ曲線（冷却）が二峰性であれば、少なくとも高温側の結晶化温度程度に冷却すればよい。一方で、最も低温側の結晶化温度程度に冷却する方法によれば、温度調整がより簡便になる。 At this time, the cooling temperature may be approximately T_cry, but if the DSC curve (cooling) is bimodal as shown in FIG. 1, cooling may be performed to at least approximately the crystallization temperature on the high temperature side. On the other hand, according to the method of cooling to about the lowest crystallization temperature, temperature adjustment becomes easier.
次に、形状Ｂの部材１０１に形状Ｃ（第３段階）を記憶させる。部材１０１に形状Ｃを記憶させる方法としては、特に制限されないが、図１で説明したＴ＿ｔｒａｎｓ１以上の温度であって、かつ、Ｔ＿ｔｒａｎｓ２未満の温度に再加熱し、形状Ｃへと変形させ、外力を維持したまま再びＴ＿ｃｒｙ程度まで冷却し形状を固定する（形状を記憶させる）ことが好ましい。 Next, the shape C (third stage) is stored in the member 101 having the shape B. The method for making the member 101 memorize the shape C is not particularly limited, but is performed by reheating the member 101 to a temperature higher than T_trans1 and lower than T_trans2 described in FIG. It is preferable to cool it again to about T_cry while maintaining the shape to fix the shape (memorize the shape).
部材１００は、すでに説明したとおり融解ピークが二峰性であるため、形状Ｃ（３段階目の形状）を記憶させるためには、低温側のＴ＿ｔｒａｎｓ１以上の温度であって、かつ、高温側のＴ＿ｔｒａｎｓ２未満の温度に再加熱すればよい。形状Ａの部材１００には上記の方法によって、形状Ｂ、及び、形状Ｃを記憶させることができる。 As already explained, the melting peak of the member 100 is bimodal, so in order to memorize the shape C (the third-stage shape), the temperature must be T_trans1 or higher on the low temperature side, and T_trans1 on the high temperature side. It may be reheated to a temperature below T_trans2. The shape B and the shape C can be stored in the member 100 having the shape A by the above method.
上記は３段階の形状記憶の例を説明したが、本部材は上記に制限されず、Ｘが３であれば４段階の形状を記憶させることができる。すなわちＸ＋１種類の形状を記憶させることができる。例えば、融解ピークが３つ以上ある場合、高温側の融解ピークの温度Ｔ＿ｔｒａｎｓＸ未満の温度であって、かつ、それより低温側のＴ＿ｔｒａｎｓ（ｘ－１）以上の温度に再加熱して形状を記憶させればよい。 Although an example of shape memory in three stages has been described above, this member is not limited to the above, and if X is 3, it is possible to memorize shapes in four stages. That is, X+1 types of shapes can be stored. For example, if there are three or more melting peaks, the shape is memorized by reheating to a temperature that is lower than the temperature T_transX of the melting peak on the high temperature side and higher than or equal to T_trans(x-1) on the lower temperature side. Just let it happen.
記憶された形状に戻すには、その形状を記憶させた際の変形温度まで、再加熱すればよい。例えば、形状Ｃである部材１０２をＴ＿ｔｒａｎｓ１以上であって、かつ、Ｔ＿ｔｒａｎｓ２未満の温度に加熱すると、記憶されていた形状Ｂへと戻すことができる。更に、形状Ｂである部材１０１をＴ＿ｔｒａｎｓ１以上の温度に加熱すると、形状Ａである部材１００が得られる。 In order to restore the memorized shape, it is sufficient to reheat it to the deformation temperature at which the shape was memorized. For example, when the member 102 having shape C is heated to a temperature of T_trans1 or higher and lower than T_trans2, it can be returned to the stored shape B. Further, when the member 101 having the shape B is heated to a temperature of T_trans1 or higher, the member 100 having the shape A is obtained.
なお、本部材の形状、及び、大きさ等は特に制限されず、用途に応じて適宜定めることができる。部材には、板、シート、及び、フィルム上の平面構造を有する成形体、３次元立体構造を有する成形体、並びに、これらの複合体を含む。 Note that the shape, size, etc. of this member are not particularly limited, and can be determined as appropriate depending on the application. The members include molded bodies having a planar structure such as plates, sheets, and films, molded bodies having a three-dimensional three-dimensional structure, and composites thereof.
〔硬化物〕
本部材は、以下の式１で表される重合性化合物を含有する組成物を硬化させてなる硬化物を含有する。本部材中における硬化物の含有量としては特に制限されないが、より優れた本発明の効果を有する部材が得られる点で、一般に部材の全質量に対して、５０～９５質量％が好ましい。なお、部材は、硬化物の１種を単独で含有してもよく、２種以上を含有していてもよい。部材が、２種以上の硬化物を含有する場合には、その合計含有量が上記数値範囲内であることが好ましい。
[Cured product]
This member contains a cured product obtained by curing a composition containing a polymerizable compound represented by the following formula 1. Although the content of the cured product in the present member is not particularly limited, it is generally preferably 50 to 95% by mass based on the total mass of the member, since a member having better effects of the present invention can be obtained. Note that the member may contain one type of cured product alone, or may contain two or more types of cured products. When the member contains two or more types of cured products, it is preferable that the total content is within the above numerical range.
＜組成物＞
上記硬化物は以下の式１で表される重合性化合物を含有する組成物を硬化させてなる。以下では、上記組成物中に含有される各成分について詳述する。
<Composition>
The cured product is obtained by curing a composition containing a polymerizable compound represented by the following formula 1. Below, each component contained in the above composition will be explained in detail.
（重合性化合物）
組成物は以下の式１で表される重合性化合物（マクロモノマー）を含有する。
(Polymerizable compound)
The composition contains a polymerizable compound (macromonomer) represented by the following formula 1.
式１中、Ｌ１はポリオキシアルキレンカルボニル基を表し、Ｘ１は重合性基を有する基を表し、Ｒ１は水素原子、又は、上記重合性基を有さない１価の置換基を表し、ｐは０以上の整数を表し、ｑは２以上の整数を表し、ｑが２かつｐが０のとき、Ｍ１は単結合、又は、２価の連結基を表し、ｑが２かつｐが１以上のとき、及び、ｑが３以上のとき、Ｍ１はｐ＋ｑ価の連結基を表し、複数あるＬ１はそれぞれ同一でも異なってもよい。 In formula 1, L 1 represents a polyoxyalkylene carbonyl group, X 1 represents a group having a polymerizable group, and R 1 represents a hydrogen atom or a monovalent substituent not having the above polymerizable group. , p represents an integer of 0 or more, q represents an integer of 2 or more, when q is 2 and p is 0, M 1 represents a single bond or a divalent linking group, and when q is 2 and p is 1 or more, and when q is 3 or more, M 1 represents a p+q-valent linking group, and each of the plurality of L 1s may be the same or different.
Ｌ１のポリオキシアルキレンカルボニル基としては特に制限されないが、以下の式２で表される基が好ましい。 The polyoxyalkylenecarbonyl group for L 1 is not particularly limited, but a group represented by the following formula 2 is preferable.
式２中、Ｌ２は分岐構造を有してもよいアルキレン基を表し、炭素数としては特に制限されないが、２～２０個が好ましく、２～１０個がより好ましい。なかでも、より優れた本発明の効果を有する部材が得られる点で、炭素数が２～１０個の直鎖状のアルキレン基が更に好ましい。
また、ｎは、２以上の数を表し、特に制限されないが、５～５０が好ましい。
また、＊は結合位置を表す。
In formula 2, L 2 represents an alkylene group which may have a branched structure, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10. Among these, a linear alkylene group having 2 to 10 carbon atoms is more preferable, since a member having better effects of the present invention can be obtained.
Further, n represents a number of 2 or more, and is not particularly limited, but preferably 5 to 50.
Moreover, * represents a bonding position.
Ｘ１の重合性基を有する基として特に制限されないが、以下の式３で表される基が好ましい。 The group having a polymerizable group for X 1 is not particularly limited, but a group represented by the following formula 3 is preferable.
式３中、Ｚは重合性基を表し、Ｌ３は単結合、又は、２価の連結基を表す。また、「＊」は結合位置を表す。
Ｌ３の２価の連結基としては特に制限されないが、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－、－ＯＣ（Ｏ）－、－Ｏ－、－Ｓ－、－ＮＲ２－（Ｒ２は水素原子又は１価の有機基を表す）、アルキレン基（炭素数１～１０個が好ましい）、シクロアルキレン基（炭素数３～１０個が好ましい）、アルケニレン基（炭素数２～１０個が好ましい）、及び、これらの組み合わせ等が挙げられる。
In formula 3, Z represents a polymerizable group, and L 3 represents a single bond or a divalent linking group. Moreover, "*" represents a bonding position.
The divalent linking group for L3 is not particularly limited, but includes -C(O)-, -C(O)O-, -OC(O)-, -O-, -S-, -NR2-(R2 represents a hydrogen atom or a monovalent organic group), alkylene group (preferably 1 to 10 carbon atoms), cycloalkylene group (preferably 3 to 10 carbon atoms), alkenylene group (preferably 3 to 10 carbon atoms), preferable), and combinations thereof.
式３中、Ｚの重合性基とは、重合反応に関与する基をいう。重合性基としては、特に制限されないが、より優れた本発明の効果を有する部材が得られる点で、ラジカル重合が可能な基が好ましく、エチレン性不飽和基がより好ましい。エチレン性不飽和基としては特に制限されないが、例えば、（メタ）アクリロイル基、スチリル基、及び、アリル基等が挙げられ、中でも、（メタ）アクリロイル基が好ましい。 In Formula 3, the polymerizable group Z refers to a group that participates in a polymerization reaction. The polymerizable group is not particularly limited, but a group capable of radical polymerization is preferable, and an ethylenically unsaturated group is more preferable, since a member having better effects of the present invention can be obtained. The ethylenically unsaturated group is not particularly limited, but includes, for example, a (meth)acryloyl group, a styryl group, an allyl group, and the like, with a (meth)acryloyl group being preferred.
式１中、Ｍ１は、ｐ＋ｑ価の連結基を表し、Ｍ１が２価の連結基である場合には、その形態としては特に制限されないが、式３のＬ３の２価の連結基としてすでに説明した基が好ましい。 In formula 1, M 1 represents a p+q valent linking group, and when M 1 is a divalent linking group, its form is not particularly limited, but it is a divalent linking group of L 3 in formula 3. The groups already explained as are preferred.
Ｍ１が３価以上の連結基である場合には、特に制限されないが、例えば、以下の式（４ａ）～（４ｄ）で表される基が挙げられる。 When M 1 is a trivalent or higher-valent linking group, it is not particularly limited, and examples thereof include groups represented by the following formulas (4a) to (4d).
式４ａ中、Ｌ３は３価の基を表す。Ｔ３は単結合又は２価の基を表し、３個のＴ３は互いに同一でも異なっていてもよい。
Ｌ３としては、窒素原子、３価の炭化水素基（炭素数１～１０個が好ましい。なお、炭化水素基は、芳香族炭化水素基でもよく脂肪族炭化水素基でもよい。）、又は、３価の複素環基（５員環～７員環の複素環基が好ましい）が挙げられ、炭化水素基にはヘテロ原子（例えば、－Ｏ－）が含まれていてもよい。Ｌ３の具体例としては、グリセリン残基、トリメチロールプロパン残基、フロログルシノール残基、及びシクロヘキサントリオール残基等が挙げられる。
In formula 4a, L 3 represents a trivalent group. T 3 represents a single bond or a divalent group, and three T 3 may be the same or different from each other.
L 3 is a nitrogen atom, a trivalent hydrocarbon group (preferably 1 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group), or Examples include trivalent heterocyclic groups (preferably 5- to 7-membered heterocyclic groups), and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of L3 include glycerin residue, trimethylolpropane residue, phloroglucinol residue, and cyclohexanetriol residue.
式４ｂ中、Ｌ４は４価の基を表す。Ｔ４は単結合又は２価の基を表し、４個のＴ４は互いに同一であってもよく異なっていてもよい。
なお、Ｌ４の好適形態としては、４価の炭化水素基（炭素数１～１０個が好ましい。なお、炭化水素基は、芳香族炭化水素基でもよく脂肪族炭化水素基でもよい。）、４価の複素環基（５～７員環の複素環基が好ましい）が挙げられ、炭化水素基にはヘテロ原子（例えば、－Ｏ－）が含まれていてもよい。Ｌ４の具体例としては、ペンタエリスリトール残基、及びジトリメチロールプロパン残基等が挙げられる。
In formula 4b, L 4 represents a tetravalent group. T 4 represents a single bond or a divalent group, and the four T 4s may be the same or different from each other.
Preferable forms of L 4 include a tetravalent hydrocarbon group (preferably 1 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group); Examples include a tetravalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group), and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of L4 include pentaerythritol residues, ditrimethylolpropane residues, and the like.
式４ｃ中、Ｌ５は５価の基を表す。Ｔ５は単結合又は２価の基を表し、５個のＴ５は互いに同一であってもよく異なっていてもよい。
なお、Ｌ５の好適形態としては、５価の炭化水素基（炭素数２～１０個が好ましい。なお、炭化水素基は、芳香族炭化水素基でもよく脂肪族炭化水素基でもよい。）、又は、５価の複素環基（５～７員環の複素環基が好ましい）が挙げられ、炭化水素基にはヘテロ原子（例えば、－Ｏ－）が含まれていてもよい。Ｌ５の具体例としては、アラビニトール残基、フロログルシドール残基、及びシクロヘキサンペンタオール残基等が挙げられる。
In formula 4c, L 5 represents a pentavalent group. T 5 represents a single bond or a divalent group, and the five T 5 may be the same or different from each other.
Preferable forms of L 5 include a pentavalent hydrocarbon group (preferably 2 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group); Alternatively, a pentavalent heterocyclic group (preferably a 5- to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of L 5 include arabinitol residue, phloroglucidol residue, and cyclohexanepentaol residue.
式４ｄ中、Ｌ６は６価の基を表す。Ｔ６は単結合又は２価の基を表し、６個のＴ６は互いに同一であってもよく異なっていてもよい。
なお、Ｌ６の好適形態としては、６価の炭化水素基（炭素数２～１０個が好ましい。なお、炭化水素基は、芳香族炭化水素基でもよく脂肪族炭化水素基でもよい。）、又は、６価の複素環基（６～７員環の複素環基が好ましい）が挙げられ、炭化水素基にはヘテロ原子（例えば、－Ｏ－）が含まれていてもよい。Ｌ６の具体例としては、マンニトール残基、ソルビトール残基、ジペンタエリスリトール残基、ヘキサヒドロキシベンゼン、及び、ヘキサヒドロキシシクロヘキサン残基等が挙げられる。
In formula 4d, L 6 represents a hexavalent group. T 6 represents a single bond or a divalent group, and the six T 6 may be the same or different from each other.
Note that preferred forms of L 6 include a hexavalent hydrocarbon group (preferably 2 to 10 carbon atoms; the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group); Alternatively, a hexavalent heterocyclic group (preferably a 6- to 7-membered heterocyclic group) may be mentioned, and the hydrocarbon group may contain a heteroatom (for example, -O-). Specific examples of L 6 include mannitol residue, sorbitol residue, dipentaerythritol residue, hexahydroxybenzene, and hexahydroxycyclohexane residue.
式４ａ～式４ｄ中、Ｔ３～Ｔ６で表される２価の基の具体例及び好適形態は、すでに説明したＬ３の２価の連結基と同様であってよい。
また、Ｍ１が７価以上の基である場合には、式４ａ～式４ｄで表した基を組み合わせた基を用いることができる。
In formulas 4a to 4d, specific examples and preferred forms of the divalent groups represented by T 3 to T 6 may be the same as the divalent linking group of L 3 described above.
Furthermore, when M 1 is a group having a valence of 7 or more, a group that is a combination of groups represented by formulas 4a to 4d can be used.
式１中、Ｒ１は水素原子、又は、上記重合性基を有さない１価の置換基を表す。重合性基を有さない１価の置換基としては特に制限されないが、例えば、＊－Ｌ４－Ｒ′で表される基が挙げられる。
上記式中、Ｌ４は、単結合、又は、２価の連結基を表し、Ｒ′は、水素原子、炭化水素基（直鎖状、分岐鎖状、若しくは、環状のいずれであってもよい）、（ポリ）オキシアルキレン基を表し、＊は結合位置を表す。
In Formula 1, R 1 represents a hydrogen atom or a monovalent substituent that does not have the above polymerizable group. The monovalent substituent having no polymerizable group is not particularly limited, but includes, for example, a group represented by *-L 4 -R'.
In the above formula, L 4 represents a single bond or a divalent linking group, and R' is a hydrogen atom or a hydrocarbon group (which may be linear, branched, or cyclic). ), represents a (poly)oxyalkylene group, and * represents the bonding position.
・重合性化合物の製造方法
重合性化合物の製造方法としては特に制限されないが、より簡便に重合性化合物が得られる点で、環状化合物を開環重合して得られた前駆体化合物に、重合性基を有する基を導入して得る方法が好ましい。
なお、前駆体化合物としては２つ以上のヒドロキシ基を有する（ポリオール化合物）ことが好ましい。
・Method for producing a polymerizable compound There are no particular restrictions on the method for producing a polymerizable compound, but in order to more easily obtain a polymerizable compound, a polymerizable compound is added to a precursor compound obtained by ring-opening polymerization of a cyclic compound. A method of introducing a group having a group is preferred.
Note that the precursor compound preferably has two or more hydroxy groups (polyol compound).
環状化合物としては公知の環状化合物を使用することができ、特に制限されないが、加水分解によって開環し得るものが好ましく、例えば、β－プロピオラクトン、β－ブチロラクトン、β－バレロラクトン、γ－ブチロラクトン、γ－バレロラクトン、γ－カプリロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、δ－ステアロラクトン、ε－カプロラクトン、γ－オクタノイックラクトン、２－メチル－ε－カプロラクトン、４－メチル－ε－カプロラクトン、ε－カプリロラクトン、ε－パルミトラクトン、α－ヒドロキシ－γ－ブチロラクトン、及び、α－メチル－γ－ブチロラクトン等の環状エステル（ラクトン化合物）；グリコリド、及び、ラクチド等の環状ジエステル；等が挙げられる。 As the cyclic compound, known cyclic compounds can be used, and although there are no particular limitations, those that can be ring-opened by hydrolysis are preferred, such as β-propiolactone, β-butyrolactone, β-valerolactone, γ- Butyrolactone, γ-valerolactone, γ-capryrolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoic lactone, 2-methyl-ε- Cyclic esters (lactone compounds) such as caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and α-methyl-γ-butyrolactone; glycolide; and cyclic diesters such as lactide.
なかでも、開環重合の反応性が良好である点で、環状化合物としては、ラクトン化合物またはラクチドが好ましく、反応性がより高く、原料の入手がより容易な点で、ラクトン化合物がより好ましく、β－プロピオラクトン、β－ブチロラクトン、β－バレロラクトン、γ－ブチロラクトン、γ－バレロラクトン、γ－カプリロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、δ－ステアロラクトン、ε－カプロラクトン、２－メチル－ε－カプロラクトン、４－メチル－ε－カプロラクトン、ε－カプリロラクトン、及び、ε－パルミトラクトンからなる群から選択される少なくとも１種であることが更に好ましい。 Among these, lactone compounds or lactide are preferable as the cyclic compound in terms of good reactivity in ring-opening polymerization, and lactone compounds are more preferable in terms of higher reactivity and easier availability of raw materials. β-propiolactone, β-butyrolactone, β-valerolactone, γ-butyrolactone, γ-valerolactone, γ-capryrolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, More preferably, it is at least one selected from the group consisting of ε-caprolactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, and ε-palmitolactone.
環状化合物を開環重合して前駆体化合物を得る方法としては特に制限されないが、金属触媒の存在下、アルコールを開始剤として開環重合する方法が挙げられる。 The method for obtaining a precursor compound by ring-opening polymerization of a cyclic compound is not particularly limited, but includes a method of ring-opening polymerization using an alcohol as an initiator in the presence of a metal catalyst.
・・金属触媒
金属触媒としては特に制限されないが、アルカリ金属、アルカリ土類金属、希土類、遷移金属類、アルミニウム、ゲルマニウム、スズ、及び、アンチモン等の脂肪酸塩、炭酸塩、硫酸塩、リン酸塩、酸化物、水酸化物、ハロゲン化物、及び、アルコラート等が挙げられる。
より具体的には、塩化第一スズ、臭化第一スズ、ヨウ化第一スズ、硫酸第一スズ、酸化第二スズ、ミリスチン酸スズ、オクチル酸スズ、ステアリン酸スズ、テトラフェニルスズ、スズメトキシド、スズエトキシド、スズブトキシド、酸化アルミニウム、アルミニウムアセチルアセトネート、アルミニウムイソプロポキシド、アルミニウム－イミン錯体、四塩化チタン、チタン酸エチル、チタン酸ブチル、チタン酸グリコール、チタンテトラブトキシド、塩化亜鉛、酸化亜鉛、ジエチル亜鉛、三酸化アンチモン、三臭化アンチモン、酢酸アンチモン、酸化カルシウム、酸化ゲルマニウム、酸化マンガン、炭酸マンガン、酢酸マンガン、酸化マグネシウム、及び、イットリウムアルコキシド等の化合物が挙げられる。
・・Metal catalyst Metal catalysts include, but are not particularly limited to, alkali metals, alkaline earth metals, rare earths, transition metals, aluminum, germanium, tin, and fatty acid salts such as antimony, carbonates, sulfates, and phosphates. , oxides, hydroxides, halides, and alcoholates.
More specifically, stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, tin tetraphenyl, tin methoxide. , tin ethoxide, tin butoxide, aluminum oxide, aluminum acetylacetonate, aluminum isopropoxide, aluminum-imine complex, titanium tetrachloride, ethyl titanate, butyl titanate, glycol titanate, titanium tetrabutoxide, zinc chloride, zinc oxide, Examples include compounds such as diethyl zinc, antimony trioxide, antimony tribromide, antimony acetate, calcium oxide, germanium oxide, manganese oxide, manganese carbonate, manganese acetate, magnesium oxide, and yttrium alkoxide.
金属触媒の使用量は金属触媒中の金属元素に換算して、環状化合物１ｋｇ当たり０．０１×１０－４～１００×１０－４モル程度が好ましい。 The amount of the metal catalyst to be used is preferably about 0.01×10 −4 to 100×10 −4 mol per kg of the cyclic compound in terms of metal elements in the metal catalyst.
・・開始剤
開始剤としては特に制限されないが、１価又は２価以上のアルコールが挙げられる。
...Initiator The initiator is not particularly limited, but monohydric or dihydric or higher alcohols may be mentioned.
１価のアルコールとしては特に制限されないが、Ｒ２－ＯＨで表されるアルコールが挙げられ、Ｒ２は、置換基を有していてもよい炭素数１～２０個の脂肪族炭化水素基を表す。
脂肪族炭化水素基としては、特に制限されないが、炭素数１～２０個のアルキル基等が挙げられる。
１価のアルコールとしては、例えば、メタノール、エタノール、ｎ－プロピルアルコール、ｎ－ブチルアルコール、ｓｅｃ－ブチルアルコール、ペンチルアルコール、ｎ－ヘキシルアルコール、シクロヘキシルアルコール、オクチルアルコール、ノニルアルコール、２－エチルヘキシルアルコール、ｎ－デシルアルコール、ｎ－ドデシルアルコール、ヘキサデシルアルコール、ラウリルアルコール、エチルラクテート、及び、ヘキシルラクテート等が挙げられる。
Monohydric alcohols are not particularly limited, but include alcohols represented by R 2 -OH, where R 2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. represent.
Examples of the aliphatic hydrocarbon group include, but are not limited to, alkyl groups having 1 to 20 carbon atoms.
Examples of monohydric alcohols include methanol, ethanol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, pentyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, octyl alcohol, nonyl alcohol, 2-ethylhexyl alcohol, Examples include n-decyl alcohol, n-dodecyl alcohol, hexadecyl alcohol, lauryl alcohol, ethyl lactate, and hexyl lactate.
また、２価以上のアルコール（多価アルコール）としては、テトラメチレングリコール、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、及び、トリメチロールメラミン等が挙げられる。
開始剤の使用量は、特に制限されないが、環状化合物１ｋｇ当たり、好ましくは０．０００１～０．０４モル程度が好ましい。
In addition, examples of alcohols having more than two valences (polyhydric alcohols) include tetramethylene glycol, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, and diglycerol. , and trimethylolmelamine.
The amount of the initiator used is not particularly limited, but is preferably about 0.0001 to 0.04 mol per kg of the cyclic compound.
・・開環重合
開環重合は、環状化合物の揮散を防ぐため、不活性ガス雰囲気下で行うことが好ましい。重合温度は、特に制限されないが、１００～２５０℃が好ましい。
重合時間としては特に制限されないが、０．１～４８時間程度が好ましい。
...Ring-opening polymerization Ring-opening polymerization is preferably carried out under an inert gas atmosphere in order to prevent volatilization of the cyclic compound. The polymerization temperature is not particularly limited, but is preferably 100 to 250°C.
The polymerization time is not particularly limited, but is preferably about 0.1 to 48 hours.
・・重合性基の導入
前駆体化合物に重合性基を導入する方法としては特に制限されないが、例えば、重合性基と、前駆体化合物の有するヒドロキシ基に対して反応性を示す置換基と、を併せて有する化合物（Ｆ１）を前駆体化合物と反応させる方法（イ）、及び、前駆体化合物が有するヒドロキシ基を他の官能基に置換し、この置換基に対して反応性を示す官能基と、重合性基とを併せて有する化合物（Ｆ２）を反応させる方法（ロ）等があげられる。なかでも、より簡便に重合性化合物（マクロモノマー）が得られる点で、（イ）の方法が好ましい。
...Introduction of polymerizable group The method of introducing a polymerizable group into the precursor compound is not particularly limited, but for example, a polymerizable group and a substituent that is reactive with the hydroxyl group of the precursor compound, A method (a) of reacting a compound (F1) having the following with a precursor compound, and substituting the hydroxy group of the precursor compound with another functional group, and a functional group showing reactivity with this substituent. Examples include a method (b) in which a compound (F2) having both a polymerizable group and a polymerizable group is reacted. Among them, method (a) is preferred because it allows a polymerizable compound (macromonomer) to be obtained more easily.
上記（イ）の方法で、前駆体化合物のヒドロキシ基と反応させるための化合物（Ｆ１）としては、特に制限されないが、例えば、重合性基が（メタ）アクリロイル基である場合、塩化（メタ）アクリル酸、及び、臭化（メタ）アクリル酸等の不飽和酸ハロゲン化合物類等が挙げられる。
前駆体化合物のヒドロキシ基と反応させる化合物（Ｆ１）の使用量としては、特に制限されないが、ヒドロキシ基に対し、０．１～１０モル当量程度が好ましい。
In the method (a) above, the compound (F1) to be reacted with the hydroxy group of the precursor compound is not particularly limited, but for example, when the polymerizable group is a (meth)acryloyl group, chloride (meth) Examples include acrylic acid and unsaturated acid halogen compounds such as brominated (meth)acrylic acid.
The amount of compound (F1) used to react with the hydroxy group of the precursor compound is not particularly limited, but is preferably about 0.1 to 10 molar equivalents to the hydroxy group.
（組成物の好適形態）
より優れた本発明の効果を有する部材が得られる点で、組成物は、式１中ｑが２である第１重合性化合物と、式１中ｑが３以上である第２重合性化合物とを含有することが好ましい。
組成物が、第１重合性化合物と第２重合性化合物とを含有することにより、得られる硬化物の結晶性がより向上し、及び／又は、得られる部材の機械的特性がより向上しやすい。
(Preferred form of composition)
In order to obtain a member having more excellent effects of the present invention, the composition comprises a first polymerizable compound in which q in formula 1 is 2, and a second polymerizable compound in which q in formula 1 is 3 or more. It is preferable to contain.
When the composition contains the first polymerizable compound and the second polymerizable compound, the crystallinity of the obtained cured product is more likely to be improved, and/or the mechanical properties of the obtained member are more likely to be improved. .
・第１重合性化合物
第１重合性化合物は式１におけるｑが２である点以外は、すでに説明した重合性化合物と同様であり、好適形態も同様である。なかでも、より優れた本発明の効果を有する部材が得られる点で、ｐは２以下が好ましく、０がより好ましい。
- First polymerizable compound The first polymerizable compound is the same as the polymerizable compound already described, except that q in Formula 1 is 2, and its preferred form is also the same. Among these, p is preferably 2 or less, and more preferably 0, since a member having better effects of the present invention can be obtained.
・第２重合性化合物
第２重合性化合物は式１におけるｑが３以上である点以外は、すでに説明した重合性化合物と同様であり、好適形態も同様である。なかでも、より優れた本発明の効果を有する部材が得られる点で、ｑは４～１０が好ましく、４～６がより好ましい。また、ｐは２以下が好ましく、０がより好ましい。
-Second polymerizable compound The second polymerizable compound is the same as the polymerizable compound already described, except that q in Formula 1 is 3 or more, and its preferred form is also the same. Among these, q is preferably 4 to 10, more preferably 4 to 6, in that a member having better effects of the present invention can be obtained. Further, p is preferably 2 or less, and more preferably 0.
組成物中における第１重合性化合物と第２重合性化合物との含有モル比としては特に制限されないが、低温側の融解ピークの温度を生体温度付近に制御しやすい点で、組成物中にける第１重合性化合物の含有量と、第２重合性化合物の含有量との合計（和）に対する、第２重合性化合物の含有量の含有モル比が０．２以上であることが好ましい。上限としては特に制限されないが、０．８以下が好ましい。
上記含有モル比が０．２以上であると、最も低温側の融解ピークを４０℃以下に調整しやすく、生体温度で応答が可能である点でより好ましい。
Although the molar ratio of the first polymerizable compound and the second polymerizable compound contained in the composition is not particularly limited, it may be included in the composition in that it is easy to control the temperature of the melting peak on the low temperature side to around the biological temperature. It is preferable that the molar ratio of the content of the second polymerizable compound to the total (sum) of the content of the first polymerizable compound and the content of the second polymerizable compound is 0.2 or more. The upper limit is not particularly limited, but is preferably 0.8 or less.
It is more preferable that the content molar ratio is 0.2 or more because the melting peak on the lowest temperature side can be easily adjusted to 40° C. or less, and response can be achieved at the body temperature.
（その他の成分）
組成物は、本発明の効果を奏する範囲内において上記以外の成分を含有していてもよい。上記以外の成分としては特に制限されないが、例えば、重合開始剤、及び、溶媒（水、有機溶媒、及び、これらの混合物等）等が挙げられる。
(Other ingredients)
The composition may contain components other than those mentioned above within a range that achieves the effects of the present invention. Components other than the above are not particularly limited, and include, for example, a polymerization initiator, a solvent (water, an organic solvent, a mixture thereof, etc.), and the like.
・重合開始剤
重合開始剤としては、特に制限されず、公知の熱重合開始剤、及び／又は、光重合開始剤が使用できる。
熱重合開始剤としては、例えば、アゾビスイソブチロニトリル等のアゾ化合物、及び、過酸化ベンゾイル等の過酸化物等が挙げられる。
光重合開始剤としては、例えば、ベンゾフェノン、ミヒラーズケトン、キサントン、及び、チオキサントン等の芳香族ケトン化合物；２－エチルアントラキノン等のキノン化合物；アセトフェノン、トリクロロアセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾインエーテル、２，２－ジエトキシアセトフェノン、及び、２，２－ジメトキシー２－フェニルアセトフェノン等のアセトフェノン化合物；メチルベンゾイルホルメート等のジケトン化合物；１－フェニル－１，２－プロパンジオン－２－（Ｏ－ベンゾイル）オキシム等のアシルオキシムエステル化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド等のアシルホスフィンオキシド化合物；テトラメチルチウラム、及び、ジチオカーバメート等のイオウ化合物；過酸化ベンゾイル等の有機化酸化物；アゾビスイソブチロニトリル等のアゾ化合物；有機スルフォニウム塩化合物；ヨードニウム塩化合物；フォスフォニウム化合物；等が挙げられる。
- Polymerization initiator The polymerization initiator is not particularly limited, and known thermal polymerization initiators and/or photopolymerization initiators can be used.
Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile, and peroxides such as benzoyl peroxide.
Examples of the photopolymerization initiator include aromatic ketone compounds such as benzophenone, Michler's ketone, xanthone, and thioxanthone; quinone compounds such as 2-ethylanthraquinone; acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, Acetophenone compounds such as 1-hydroxycyclohexylphenyl ketone, benzoin ether, 2,2-diethoxyacetophenone, and 2,2-dimethoxy2-phenylacetophenone; diketone compounds such as methylbenzoylformate; 1-phenyl-1,2 - Acyl oxime ester compounds such as propanedione-2-(O-benzoyl) oxime; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; sulfur compounds such as tetramethylthiuram and dithiocarbamate; Examples include organic oxides such as benzoyl peroxide; azo compounds such as azobisisobutyronitrile; organic sulfonium salt compounds; iodonium salt compounds; and phosphonium compounds.
重合開始剤は、１種を単独で又は２種以上を組み合わせて使用できる。組成物中における重合開始剤の含有量は、組成物の全質量に対して、０．００１～１０質量％が好ましい。 One type of polymerization initiator can be used alone or two or more types can be used in combination. The content of the polymerization initiator in the composition is preferably 0.001 to 10% by mass based on the total mass of the composition.
組成物を硬化させる方法としては特に制限されず、公知の硬化方法が使用できる。なかでも、より簡便に部材が得られる点で、上記組成物にエネルギー付与（加熱、及び／又は、光照射）することが好ましい。 The method for curing the composition is not particularly limited, and any known curing method can be used. Among these, it is preferable to impart energy (heating and/or light irradiation) to the composition, since the member can be obtained more easily.
〔高分子化合物〕
本部材は、オキシアルキレンカルボニル基からなる繰り返し単位（以下「特定単位」ともいう。）を有する高分子化合物（特定高分子化合物）を含有する。本部材中における特定高分子化合物の含有量としては特に制限されないが、より優れた本発明の効果を有する部材が得られる点で、一般に部材の全質量に対して、１～５０質量％が好ましい。なお、部材は、特定高分子化合物の１種を単独で含有してもよく、２種以上を含有していてもよい。部材が、２種以上の高分子化合物を含有する場合には、その合計含有量が上記数値範囲内であることが好ましい。
[Polymer compound]
This member contains a polymer compound (specific polymer compound) having a repeating unit (hereinafter also referred to as "specific unit") consisting of an oxyalkylene carbonyl group. The content of the specific polymer compound in this member is not particularly limited, but it is generally preferred to be 1 to 50% by mass based on the total mass of the member, since a member having better effects of the present invention can be obtained. . Note that the member may contain one type of specific polymer compound alone, or may contain two or more types of specific polymer compounds. When the member contains two or more types of polymer compounds, it is preferable that the total content is within the above numerical range.
なお、本明細書において、特定高分子化合物は、重合性基を有しない化合物であり、すでに説明した重合性化合物の硬化物とは異なる化合物を意図する。 Note that in this specification, the specific polymer compound is a compound that does not have a polymerizable group, and is intended to be a compound that is different from the cured product of the polymerizable compound described above.
特定単位としては、以下の式５で表される単位が挙げられる。
式２中、Ｌ５は分岐構造を有してもよいアルキレン基を表し、炭素数としては特に制限されないが、２～２０個が好ましく、２～１０個がより好ましい。なかでも、より優れた本発明の効果を有する部材が得られる点で、炭素数が２～１０個の直鎖状のアルキレン基が更に好ましい。 In formula 2, L 5 represents an alkylene group which may have a branched structure, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10. Among these, a linear alkylene group having 2 to 10 carbon atoms is more preferable, since a member having better effects of the present invention can be obtained.
なお、Ｌ５のアルキレン基は、すでに説明したＬ２のアルキレン基と同一の基であることが好ましい。Ｌ２とＬ５とが同一の基であると、硬化物（又は重合性化合物）と特定高分子化合物とのより優れた相溶性が得られる。 In addition, it is preferable that the alkylene group of L5 is the same group as the alkylene group of L2 already explained. When L 2 and L 5 are the same group, better compatibility between the cured product (or polymerizable compound) and the specific polymer compound can be obtained.
特定高分子化合物の分子量としては特に制限されないが、より優れた本発明の効果を有する部材が得られる点で、２０００～１０００００が好ましく、５０００～８００００がより好ましい。
なお、本明細書において、分子量とは、ゲル浸透クロマトグラフィー法により測定したＰＥＧ（ポリエチレングリコール）スタンダード換算の数平均分子量を意味する。
The molecular weight of the specific polymer compound is not particularly limited, but it is preferably from 2,000 to 100,000, more preferably from 5,000 to 80,000, since a member having better effects of the present invention can be obtained.
In addition, in this specification, the molecular weight means the number average molecular weight in terms of a PEG (polyethylene glycol) standard measured by gel permeation chromatography.
特に制限されないが、より優れた本発明の効果を有する部材が得られる点で、特定高分子化合物は、環状化合物を開環重合して得られたものであることが好ましい。 Although not particularly limited, it is preferable that the specific polymer compound is obtained by ring-opening polymerization of a cyclic compound, since a member having better effects of the present invention can be obtained.
環状化合物としては公知の環状化合物を使用することができ、特に制限されないが、加水分解によって開環し得るものが好ましく、例えば、β－プロピオラクトン、β－ブチロラクトン、β－バレロラクトン、γ－ブチロラクトン、γ－バレロラクトン、γ－カプリロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、δ－ステアロラクトン、ε－カプロラクトン、γ－オクタノイックラクトン、２－メチル－ε－カプロラクトン、４－メチル－ε－カプロラクトン、ε－カプリロラクトン、ε－パルミトラクトン、α－ヒドロキシ－γ－ブチロラクトン、及び、α－メチル－γ－ブチロラクトン等の環状エステル（ラクトン化合物）；グリコリド、及び、ラクチド等の環状ジエステル；等が挙げられる。
なお、特定高分子化合物は、環状化合物の１種を単独で開環重合したものであってもよく、２種以上を用いて共重合したものであってもよい。その場合、２種以上の環状化合物に基づく単位の特定高分子化合物中における配列は、ランダムであっても、ブロックであってもよい。
As the cyclic compound, known cyclic compounds can be used, and although there are no particular limitations, those that can be ring-opened by hydrolysis are preferred, such as β-propiolactone, β-butyrolactone, β-valerolactone, γ- Butyrolactone, γ-valerolactone, γ-capryrolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoic lactone, 2-methyl-ε- Cyclic esters (lactone compounds) such as caprolactone, 4-methyl-ε-caprolactone, ε-caprylolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and α-methyl-γ-butyrolactone; glycolide; and cyclic diesters such as lactide.
The specific polymer compound may be obtained by ring-opening polymerization of one type of cyclic compound alone, or may be obtained by copolymerizing two or more types of cyclic compounds. In that case, the arrangement of units based on two or more types of cyclic compounds in the specific polymer compound may be random or block.
なかでもより優れた本発明の効果を有する部材が得られる点で、特定高分子化合物は、β－プロピオラクトン、β－ブチロラクトン、β－バレロラクトン、γ－ブチロラクトン、γ－バレロラクトン、γ－カプリロラクトン、δ－バレロラクトン、β－メチル－δ－バレロラクトン、δ－ステアロラクトン、ε－カプロラクトン、γ－オクタノイックラクトン、２－メチル－ε－カプロラクトン、４－メチル－ε－カプロラクトン、ε－カプリロラクトン、ε－パルミトラクトン、α－ヒドロキシ－γ－ブチロラクトン、及び、α－メチル－γ－ブチロラクトン等の環状エステル（ラクトン化合物）；グリコリド、及び、ラクチド等の環状ジエステル；等を開環重合して得られたものであることが好ましい。 Among them, the specific polymer compounds include β-propiolactone, β-butyrolactone, β-valerolactone, γ-butyrolactone, γ-valerolactone, γ- Capryrolactone, δ-valerolactone, β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoic lactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone , cyclic esters (lactone compounds) such as ε-capryrolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone, and α-methyl-γ-butyrolactone; cyclic diesters such as glycolide and lactide; etc. It is preferable that the compound be obtained by ring-opening polymerization.
なかでも、より優れた本発明の効果を有する部材が得られる点で、特定高分子化合物としては、環状化合物を開環重合して得られた直鎖状の高分子であることが好ましい。特定高分子化合物は上記以外の繰り返し単位を含有していてもよい。 Among these, the specific polymer compound is preferably a linear polymer obtained by ring-opening polymerization of a cyclic compound, since a member having better effects of the present invention can be obtained. The specific polymer compound may contain repeating units other than those mentioned above.
〔その他の成分〕
本部材は本発明の効果を奏する範囲内において、特定硬化物、及び、特定高分子化合物以外のその他の成分を含有していてもよい。その他の成分としては例えば、薬剤；磁場操作を可能とするための磁性粒子；光駆動を可能とするための金ナノロッド、及び、窒化チタン等の光熱変換材料；イメージングのための半導体粒子；ジュール熱駆動、及び、力学物性改変のための他の（液体）金属・無機材料等；粘土鉱物（力学物性改変）等が挙げられる。
[Other ingredients]
This member may contain other components other than the specific cured product and the specific polymer compound within the range where the effects of the present invention are achieved. Other components include, for example, drugs; magnetic particles to enable magnetic field manipulation; photothermal conversion materials such as gold nanorods and titanium nitride to enable optical drive; semiconductor particles for imaging; Joule heat Other (liquid) metals, inorganic materials, etc. for driving and modifying mechanical properties; clay minerals (for modifying mechanical properties), etc.
・薬剤
薬剤としては、特に制限されないが、抗がん剤、免疫抑制剤、抗生物質、抗リウマチ剤、抗血栓薬、ＨＭＧ－ＣｏＡ還元酵素阻害剤、ＡＣＥ阻害剤、アンギオテンシンＩＩ受容体拮抗薬、ＮＯ供与剤、カルシウム拮抗薬、抗高脂血症薬、抗炎症剤、インテグリン阻害薬、抗アレルギー剤、抗酸化剤、ＧＰＩＩｂＩＩＩａ拮抗薬、レチノイド、フラボノイド、カロチノイド、脂質改善薬、ＤＮＡ合成阻害剤、チロシンキナーゼ阻害剤、抗血小板薬、血管平滑筋増殖抑制薬、血管造影剤、インターフェロン、成長因子、及び、これらの組み合わせ等が挙げられる。
部材は薬剤の１種を単独で含有してもよく、２種以上を併せて含有していてもよい。
・Drugs Drugs include, but are not particularly limited to, anticancer drugs, immunosuppressants, antibiotics, antirheumatic drugs, antithrombotic drugs, HMG-CoA reductase inhibitors, ACE inhibitors, angiotensin II receptor antagonists, NO donor, calcium antagonist, antihyperlipidemic agent, anti-inflammatory agent, integrin inhibitor, antiallergic agent, antioxidant, GPIIbIIIa antagonist, retinoid, flavonoid, carotenoid, lipid improving agent, DNA synthesis inhibitor, Examples include tyrosine kinase inhibitors, antiplatelet drugs, vascular smooth muscle proliferation inhibitors, angiographic agents, interferons, growth factors, and combinations thereof.
The member may contain one type of drug alone, or may contain two or more types in combination.
〔部材の用途〕
本部材は、３段階の形状を記憶できるため医療用ステント材料、アクチュエーター、及び、ウェアラブルデバイス等に応用可能である。
[Uses of parts]
Since this member can memorize three stages of shapes, it can be applied to medical stent materials, actuators, wearable devices, etc.
［部材の製造方法］
本部材の製造方法としては特に制限されないが、すでに説明した各成分を混合することにより製造可能である。なかでも、より簡便に部材を製造できる点で、部材の製造方法としては、すでに説明した式１で表される重合性化合物を含有する組成物と、オキシアルキレンカルボニル基からなる繰り返し単位を有する高分子化合物と、を混合して混合物を得て、上記混合物にエネルギーを付与して上記組成物を硬化させて部材を得る、部材の製造方法であることが好ましい。
[Manufacturing method of parts]
Although there are no particular restrictions on the method for manufacturing this member, it can be manufactured by mixing the components already described. Among these, the method for producing the member is based on a composition containing the polymerizable compound represented by the formula 1 described above and a polymer having a repeating unit consisting of an oxyalkylene carbonyl group, since the member can be manufactured more easily. It is preferable that the method for producing a member is such that a mixture is obtained by mixing a molecular compound and a member is obtained by applying energy to the mixture to cure the composition.
上記の方法であれば、所望の形状の部材が得られやすい。すなわち、混合物をモールド等に注入し、その後、組成物を硬化させることにより、硬化物と高分子化合物とを有する部材が得られる。なお、硬化物を得る方法等についてすでに説明したとおりであり、好適形態も同様である。 With the above method, it is easy to obtain a member having a desired shape. That is, by injecting the mixture into a mold or the like and then curing the composition, a member having a cured product and a polymer compound can be obtained. Note that the method for obtaining the cured product and the like have already been explained, and the preferred form is also the same.
以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be explained in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.
［実施例１：部材１の調製］
〔マクロモノマー（４ｂ１０－ｍ）の合成〕
まず、ペンタエリスリトールを１２時間減圧乾燥した。次に、三口フラスコに、ε－カプロラクトン（１１４．１４ｇ、東京化成工業社製）、及び、ペンタエリスリトール（３．４０ｇ、東京化成工業社製）を導入し、窒素を吹き込みながら、混合物を攪拌した。次に、混合物にオクタン酸錫（１－１．５ｇ）を加え、得られた混合物を１２０℃で２４時間保持して、末端に４つのヒドロキシ基を有する前駆体化合物を得た。次に、前駆体化合物の末端を塩化アクリロイルと反応させてアクリロイル基を有するマクロモノマーを得た。このマクロモノマーの分岐鎖の重合度は１０であり、これを「４ｂ１０－ｍ」と命名した。上記のスキームを以下の式に示した。
なお、このマクロモノマーの構造、及び、分子量はプロトン核磁気共鳴分光法、及び、ゲル浸透クロマトグラフィー法により測定、及び、推定した。
[Example 1: Preparation of member 1]
[Synthesis of macromonomer (4b10-m)]
First, pentaerythritol was dried under reduced pressure for 12 hours. Next, ε-caprolactone (114.14 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) and pentaerythritol (3.40 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were introduced into a three-necked flask, and the mixture was stirred while blowing nitrogen. . Next, tin octoate (1-1.5 g) was added to the mixture, and the resulting mixture was held at 120° C. for 24 hours to obtain a precursor compound having four hydroxy groups at the ends. Next, the terminal end of the precursor compound was reacted with acryloyl chloride to obtain a macromonomer having an acryloyl group. The degree of polymerization of the branched chain of this macromonomer was 10, and it was named "4b10-m". The above scheme is shown in the following formula.
The structure and molecular weight of this macromonomer were measured and estimated by proton nuclear magnetic resonance spectroscopy and gel permeation chromatography.
〔マクロモノマー（２ｂ２０－ｍ）の合成〕
ペンタエリスリトールに代えて、テトラメチレングリコール（ブタンジオール）を用いたこと以外は４ｂ１０－ｍの合成と同様にして「２ｂ２０－ｍ」を下記スキームに基づき合成した。
[Synthesis of macromonomer (2b20-m)]
"2b20-m" was synthesized based on the following scheme in the same manner as the synthesis of 4b10-m, except that tetramethylene glycol (butanediol) was used instead of pentaerythritol.
〔部材１の合成〕
以下の成分を混合し、キシレンに溶解させ、混合物を調製した。次に、ポリテトラフルオロエチレン製スペーサを介して対向する一対のガラス基板の間に混合物を注液し、８０℃で３時間加熱して部材１を得た。なお、部材１はアセトンを用いて５回洗浄した後、メタノールに浸漬し、その後、減圧乾燥した（オーバーナイト）。
＜混合物の組成（固形分）＞
・４ｂ１０－ｍ ０．２ｇ
・２ｂ２０－ｍ ０．３ｇ
・Ｌ－ＰＣＬ（高分子化合物に該当する。Ｓｉｇｍａ－Ａｌｄｒｉｃｈ社製， Ｍｎ＝８０，０００、直鎖状であり、分子鎖末端を含め、分子内に重合性基を有さない。） ０．１５ｇ
・過酸化ベンゾイル ０．０２５ｇ
[Synthesis of member 1]
A mixture was prepared by mixing the following ingredients and dissolving them in xylene. Next, the mixture was injected between a pair of glass substrates facing each other via a polytetrafluoroethylene spacer, and heated at 80° C. for 3 hours to obtain member 1. Note that member 1 was washed five times using acetone, immersed in methanol, and then dried under reduced pressure (overnight).
<Composition of mixture (solid content)>
・4b10-m 0.2g
・2b20-m 0.3g
・L-PCL (corresponds to a polymer compound. Manufactured by Sigma-Aldrich, Mn=80,000, linear, and does not have a polymerizable group in the molecule, including the molecular chain terminal.) 0. 15g
・Benzoyl peroxide 0.025g
なお、マクロモノマー（４ｂ１０－ｍ）、及び、マクロモノマー（２ｂ２０－ｍ）の理論分子量は略同様であるたの、上記混合物中における両者の含有質量比は、含有モル比と同様である。 Note that although the theoretical molecular weights of the macromonomer (4b10-m) and the macromonomer (2b20-m) are approximately the same, the mass ratio of the two in the above mixture is the same as the molar ratio of the two.
［比較例１：比較部材の合成］
Ｌ－ＰＣＬを用いなかったこと以外は、部材１の合成方法と同様にして、比較部材を合成した。なお、混合物の組成は以下のとおりだった。
＜混合物の組成（固形分）＞
・４ｂ１０－ｍ ０．１５ｇ
・２ｂ２０－ｍ ０．３５ｇ
・過酸化ベンゾイル ０．０２５ｇ
[Comparative Example 1: Synthesis of comparative members]
A comparative member was synthesized in the same manner as the method for synthesizing member 1, except that L-PCL was not used. The composition of the mixture was as follows.
<Composition of mixture (solid content)>
・4b10-m 0.15g
・2b20-m 0.35g
・Benzoyl peroxide 0.025g
［示差走査熱量測定］
部材１、及び、比較部材について、示差走査熱量分析計（エスアイアイ社製、「Ｘ－ＤＳＣ ７０００」）を用いて、昇温過程（ｈｅａｔｉｎｇ）及び冷却過程（ｃｏｏｌｉｎｇ）の測定を行った。なお、昇温（冷却）速度は５℃／分とした。
図３には、部材１の示差走査熱量測定結果を示した。横軸が時間、縦軸は負（下）方向に吸熱（「Ｅｎｄｏｔｈｅｒｍ」）量を示している。また、図３中「ｈｅａｔｉｎｇ」とあるのは昇温過程を示し、「ｃｏｏｌｉｎｇ」とあるのは、冷却過程を示している。
図３によれば、部材１は、３７℃（Ｔ＿ｔｒａｎｓ１）と５１℃（Ｔ＿ｔｒａｎｓ２）とに融解ピークを有する二峰性であることがわかった。
なお、図３中「４ｂ／２ｂ＝４０／６０－ｌＰＣＬ」とあるのは、４ｂ１０／２ｂ２０／Ｌ－ＰＣＬが質量比で０．２ｇ／０．３ｇ／０．１５ｇであることを示している（４ｂ１０と２ｂ２０の比率は、モル比も同様である）。
[Differential scanning calorimetry]
Regarding the member 1 and the comparative member, the heating process (heating) and the cooling process (cooling) were measured using a differential scanning calorimeter (manufactured by SII Inc., "X-DSC 7000"). Note that the heating (cooling) rate was 5° C./min.
FIG. 3 shows the results of differential scanning calorimetry of member 1. The horizontal axis represents time, and the vertical axis represents the amount of endotherm in the negative (downward) direction. Further, in FIG. 3, "heating" indicates a temperature raising process, and "cooling" indicates a cooling process.
According to FIG. 3, member 1 was found to be bimodal with melting peaks at 37°C (T_trans1) and 51°C (T_trans2).
In addition, "4b/2b=40/60-1PCL" in FIG. 3 indicates that 4b10/2b20/L-PCL has a mass ratio of 0.2g/0.3g/0.15g. (The molar ratio of 4b10 and 2b20 is also the same).
図４には、比較部材の示差走査熱量測定結果を示した。縦軸、横軸、及び、注釈等の意義は図１と同様である。図４の結果から、比較部材は３８℃に単一の融解ピークを有することがわかった。なお、図２中、「４ｂ／２ｂ＝３０／７０」とあるのは、４ｂ１０／２ｂ２０が質量比（モル比）で０．１５ｇ／０．３５ｇであることを示している。 FIG. 4 shows the results of differential scanning calorimetry of the comparison member. The meanings of the vertical axis, horizontal axis, annotations, etc. are the same as in FIG. From the results in FIG. 4, it was found that the comparative member had a single melting peak at 38°C. In addition, in FIG. 2, "4b/2b=30/70" indicates that the mass ratio (mole ratio) of 4b10/2b20 is 0.15 g/0.35 g.
［Ｘ線回折強度測定］
部材１、及び、比較部材について、Ｘ線回折装置（Ｒｉｇａｋｕ社製、「ＳｍａｒｔＬａｂ」）を使用し、４５ｋＶ、２００ｍＡを付加したＣｕＫαのＸ線を入射し、回折角２θが５～４０度の回折強度分布を測定した。この時、測定を２５℃から開始し、２℃毎に７０℃まで、温度を２℃／ステップで変化させながら測定した。
具体的には、２５℃の次は、２８℃に加温し、１０分ホールド後に測定し、測定終了後は、２℃毎に加温、１０分ホールド、測定を繰り返した。
また、回折ピークの面積から、結晶化度を算出し、横軸を測定温度としてプロットした。
[X-ray diffraction intensity measurement]
Regarding the member 1 and the comparative member, using an X-ray diffraction device (manufactured by Rigaku, "SmartLab"), CuKα X-rays with 45 kV and 200 mA were applied, and the diffraction angle 2θ was 5 to 40 degrees. The intensity distribution was measured. At this time, the measurement was started from 25°C and was carried out while changing the temperature at 2°C/step up to 70°C.
Specifically, after 25° C., the temperature was heated to 28° C., held for 10 minutes, and then measured. After the measurement was completed, heating was performed every 2° C., held for 10 minutes, and the measurement was repeated.
Further, the degree of crystallinity was calculated from the area of the diffraction peak, and the horizontal axis was plotted with the measurement temperature.
図５には、部材１のＸ線回折強度分布を示した。横軸は回折角２θし（°）、縦軸は回折強度を示している。また、図６には、図５の回折強度分布から算出した結晶化度を示した。図６の横軸は測定温度を示し、縦軸は結晶化度（％）を示している。
図５及び図６に示した結果から、部材１が２段階の温度応答を示すことが確認された。
FIG. 5 shows the X-ray diffraction intensity distribution of member 1. The horizontal axis represents the diffraction angle 2θ (°), and the vertical axis represents the diffraction intensity. Further, FIG. 6 shows the degree of crystallinity calculated from the diffraction intensity distribution of FIG. 5. The horizontal axis of FIG. 6 shows the measurement temperature, and the vertical axis shows the degree of crystallinity (%).
From the results shown in FIGS. 5 and 6, it was confirmed that member 1 exhibited a two-stage temperature response.
図７には、比較部材のＸ線回折強度分布を示した。また、図８には、図７の回折強度分布から算出した結晶化度を示した。図７及び図８に示した結果から、比較部材は２段階の温度応答を示さないことが確認された。 FIG. 7 shows the X-ray diffraction intensity distribution of the comparison member. Further, FIG. 8 shows the degree of crystallinity calculated from the diffraction intensity distribution of FIG. 7. From the results shown in FIGS. 7 and 8, it was confirmed that the comparative member did not exhibit a two-step temperature response.
［形状記憶能の確認］
部材１（図９、１段階目、長さ約３５ｍｍ×幅約６ｍｍ×厚み約０．２ｍｍ）を６０℃に加熱し、変形させた状態で４℃へと冷却した。この時、部材１は図１０（２段階目）の状態であった。次に、部材１を４０℃に加熱し、変形させて４℃へと冷却した。このとき、部材１は図１１（３段階目）の状態であった。
その後、部材１を４０℃に加熱したところ、部材１は、図１１（３段階目）の状態から、図１２の状態（２段階目）に変化した。次に、図１２の状態の部材１を、６０℃に加熱したところ、部材１は図１３の状態（１段階目）に変化した。
図９～図１３に示した結果から、部材１は３段階の形状記憶能を有することがわかった。
[Checking shape memory ability]
Member 1 (FIG. 9, first stage, length about 35 mm x width about 6 mm x thickness about 0.2 mm) was heated to 60°C and cooled to 4°C in a deformed state. At this time, the member 1 was in the state shown in FIG. 10 (second stage). Next, member 1 was heated to 40°C, deformed, and cooled to 4°C. At this time, the member 1 was in the state shown in FIG. 11 (third stage).
Thereafter, when the member 1 was heated to 40° C., the member 1 changed from the state shown in FIG. 11 (third stage) to the state shown in FIG. 12 (second stage). Next, when the member 1 in the state shown in FIG. 12 was heated to 60° C., the member 1 changed to the state shown in FIG. 13 (first stage).
From the results shown in FIGS. 9 to 13, it was found that member 1 had three levels of shape memory ability.
比較部材について、融点以上の温度に加熱し、ひずみを与えたまま結晶化温度以下へと冷却し、その後、融点以上の温度に加熱したところ、元の形状に戻ったが、２段階の形状記憶能しか有しておらず、３段階の形状記憶能を有していなかった。 When the comparison member was heated to a temperature above the melting point, cooled to below the crystallization temperature while being strained, and then heated to a temperature above the melting point, it returned to its original shape, but the two-step shape memory However, it did not have three levels of shape memory ability.
［低温側融解ピークの調整］
部材１と同様の方法を用いて、４ｂ１０－ｍと２ｂ２０－ｍのモル比（質量比）を変化させた種々の部材を調製し、示差走査熱量測定を行った。結果を図１４に示した。
図１４において、横軸は、組成物中における４ｂ１０－ｍの含有量と２ｂ２０－ｍの含有量との合計に対する４ｂ１０－ｍの含有量の含有モル比（％）を示し、
縦軸は低温側の融解ピーク（第１（左）軸、「丸」でプロットされたデータに対応）、及び、エンタルピー変化（第２（右）軸、「三角」でプロットされたデータに対応）を示している。
図１４の結果から、組成物中における４ｂ１０－ｍの含有量と２ｂ２０－ｍの含有量との合計に対する４ｂ１０－ｍの含有量の含有モル比が０．２（２０％）以上であると低温側の融解ピークが４０℃以下となることがわかった。低温側の融解ピークが４０℃以下となることにより、生体温度において、形状記憶能を発揮することができるため、より優れている。
[Adjustment of low temperature side melting peak]
Using the same method as for Member 1, various members were prepared with varying molar ratios (mass ratios) of 4b10-m and 2b20-m, and differential scanning calorimetry was performed. The results are shown in FIG.
In FIG. 14, the horizontal axis indicates the molar ratio (%) of the content of 4b10-m to the total of the content of 4b10-m and the content of 2b20-m in the composition,
The vertical axis shows the melting peak on the low temperature side (first (left) axis, corresponding to data plotted as "circle") and enthalpy change (second (right) axis, corresponding to data plotted as "triangle"). ) is shown.
From the results in FIG. 14, it can be seen that when the molar ratio of the content of 4b10-m to the total of the content of 4b10-m and the content of 2b20-m in the composition is 0.2 (20%) or more, the temperature is low. It was found that the melting peak on the side was 40°C or lower. Since the melting peak on the low-temperature side is 40° C. or lower, it is possible to exhibit shape memory ability at biological temperature, which is more excellent.
１００、１０１、１０２ 部材
100, 101, 102 members
Claims (14)
オキシアルキレンカルボニル基からなる繰り返し単位を有し、結晶性を有する高分子化合物とを含有する部材。
Ｌ１はポリオキシアルキレンカルボニル基を表し、Ｘ１は重合性基を有する基を表し、Ｒ１は水素原子、又は、前記重合性基を有さない１価の置換基を表し、ｑは２以上の整数を表し、ｐは０以上の整数を表し、
ｑが２かつｐが０のとき、Ｍ１ は２価の連結基を表し、
ｑが２かつｐが１以上のとき、及び、ｑが３以上のとき、Ｍ１はｐ＋ｑ価の連結基を表し、
複数あるＬ１はそれぞれ同一でも異なってもよい。） A cured product having crystallinity obtained by curing a composition containing a polymerizable compound represented by Formula 1,
A member containing a crystalline polymer compound having a repeating unit consisting of an oxyalkylene carbonyl group.
L 1 represents a polyoxyalkylene carbonyl group, X 1 represents a group having a polymerizable group, R 1 represents a hydrogen atom or a monovalent substituent not having the polymerizable group, and q represents 2 p represents an integer greater than or equal to 0, p represents an integer greater than or equal to 0,
When q is 2 and p is 0, M 1 represents a divalent linking group,
When q is 2 and p is 1 or more, and when q is 3 or more, M 1 represents a p + q-valent linking group,
The plurality of L1s may be the same or different. )
（式３中、Ｚは重合性基を表し、Ｌ３は単結合、又は、２価の連結基を表す。また、「＊」は結合位置を表す。） The member according to any one of claims 1 to 8, wherein the group having a polymerizable group is a group represented by formula 3.
(In Formula 3, Z represents a polymerizable group, L3 represents a single bond or a divalent linking group. Also, "*" represents a bonding position.)
（式２中、Ｌ２は分岐構造を有してもよいアルキレン基を表し、＊は結合位置を表し、ｎは２以上の数を表す。） The member according to any one of claims 1 to 9, wherein the polyoxyalkylenecarbonyl group is a group represented by formula 2.
(In Formula 2, L2 represents an alkylene group that may have a branched structure, * represents a bonding position, and n represents a number of 2 or more.)
Ｌ１はポリオキシアルキレンカルボニル基を表し、Ｘ１は重合性基を有する基を表し、Ｒ１は水素原子、又は、前記重合性基を有さない１価の置換基を表し、ｑは２以上の整数を表し、ｐは０以上の整数を表し、
ｑが２かつｐが０のとき、Ｍ１ は２価の連結基を表し、
ｑが２かつｐが１以上のとき、及び、ｑが３以上のとき、Ｍ１はｐ＋ｑ価の連結基を表し、
複数あるＬ１はそれぞれ同一でも異なってもよい。） A composition containing the polymerizable compound represented by Formula 1 and a polymer compound having a repeating unit consisting of an oxyalkylene carbonyl group are mixed to obtain a mixture, and energy is imparted to the mixture to form the composition. A method for producing a member, comprising curing the product to obtain the member according to any one of claims 1 to 13.
L 1 represents a polyoxyalkylene carbonyl group, X 1 represents a group having a polymerizable group, R 1 represents a hydrogen atom or a monovalent substituent not having the polymerizable group, and q represents 2 p represents an integer greater than or equal to 0, p represents an integer greater than or equal to 0,
When q is 2 and p is 0, M 1 represents a divalent linking group,
When q is 2 and p is 1 or more, and when q is 3 or more, M 1 represents a p + q-valent linking group,
A plurality of L1s may be the same or different. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019169340A JP7371890B2 (en) | 2019-09-18 | 2019-09-18 | Components and methods of manufacturing components |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019169340A JP7371890B2 (en) | 2019-09-18 | 2019-09-18 | Components and methods of manufacturing components |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021046481A JP2021046481A (en) | 2021-03-25 |
| JP7371890B2 true JP7371890B2 (en) | 2023-10-31 |
Family
ID=74877803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019169340A Active JP7371890B2 (en) | 2019-09-18 | 2019-09-18 | Components and methods of manufacturing components |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7371890B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021200532A1 (en) * | 2020-04-01 | 2021-10-07 | 国立研究開発法人物質・材料研究機構 | Member, method for manufacturing member, method for manufacturing permanent-shape-changed member, permanent-shape-changed member, cell culture substrate, ligation device, and laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002504585A (en) | 1998-02-23 | 2002-02-12 | ニーモサイエンス ゲーエムベーハー | Shape memory polymer |
| JP2021023499A (en) | 2019-08-02 | 2021-02-22 | 国立研究開発法人物質・材料研究機構 | Thermoplastic shape memory resin sheet and article including thermoplastic shape memory resin sheet |
-
2019
- 2019-09-18 JP JP2019169340A patent/JP7371890B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002504585A (en) | 1998-02-23 | 2002-02-12 | ニーモサイエンス ゲーエムベーハー | Shape memory polymer |
| JP2021023499A (en) | 2019-08-02 | 2021-02-22 | 国立研究開発法人物質・材料研究機構 | Thermoplastic shape memory resin sheet and article including thermoplastic shape memory resin sheet |
Non-Patent Citations (1)
| Title |
|---|
| Mitsuhiro Ebara, Koichiro Uto, Naokazu Idota, John M. Hoffman, and Takao Aoyagi，Shape-Memory Surface with Dynamically Tunable Nanogeometry Activated by Body Heat，Advanced Materials，ドイツ，Wiley-VCH，2012年，24(2)，273-278 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021046481A (en) | 2021-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hong et al. | “Nonstrained” γ-butyrolactone-based copolyesters: copolymerization characteristics and composition-dependent (thermal, eutectic, cocrystallization, and degradation) properties | |
| JPS60101118A (en) | Biologically reabsorptive polyester and polyester composition | |
| KR20130118214A (en) | Polylactic acid block copolymer | |
| JP7371890B2 (en) | Components and methods of manufacturing components | |
| JP2013507495A (en) | Process for producing polyesters and copolyesters from lactones | |
| WO2004033528A1 (en) | High-molecular aliphatic polyester and process for producing the same | |
| JP2000311516A (en) | Polymeric solid electrolyte | |
| US7772362B2 (en) | Treatment method for imparting self-healing and shape memory properties to certain CBDO copolymers | |
| JP2014227452A (en) | Polylactic acid-based resin | |
| CN109810246A (en) | A kind of low temperature polycaprolactone preparation method that fusing point is controllable | |
| TWI276642B (en) | Nucleophilic acyl substituting polymerizations catalyzed by metal oxide complex | |
| US20210355271A1 (en) | Bifuran polyesters | |
| CN114456561A (en) | Polymer compositions containing PBSA plasticizer | |
| JP7403790B2 (en) | Composition, cured product, method for producing cured product, wearable device, method for attaching wearable device, method for removing wearable device, method for using wearable device, and band | |
| JP7274241B2 (en) | Member, method of manufacturing member, method of manufacturing permanent reshaped member, permanent reshaped member, cell culture substrate, ligation device, and laminate | |
| TW201245208A (en) | Method for preparing poly(1,4:3,6-dianhydrohexitol esters) | |
| CN109096478A (en) | A kind of Aliphatic Polycarbonate Copolymers and preparation method thereof | |
| JP2009242444A (en) | Method for producing polylactic acid block copolymer | |
| JP2009242443A (en) | Polylactic acid block copolymer, method for producing it, and molded product | |
| JP2022153686A (en) | Cured product, shape-memory member, ligator, suture, and wearable device | |
| JP7302296B2 (en) | Polyester copolymer and method for producing same | |
| JP2008050433A (en) | Method for manufacturing copolyester film adhesive material | |
| JP4766893B2 (en) | Polymer and production method thereof | |
| CN115667361A (en) | Autocatalytic rapid degradation polyester polymer and preparation method and application thereof | |
| Liu et al. | Synthesis of poly (ethylene adipate-co-l-lactic acid) copolymers via ring opening polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220727 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230517 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230530 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230718 |
|
| 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: 20231003 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20231012 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7371890 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |