JP2006002087A - Resin composition for optical solid creation - Google Patents
Resin composition for optical solid creation Download PDFInfo
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- JP2006002087A JP2006002087A JP2004181593A JP2004181593A JP2006002087A JP 2006002087 A JP2006002087 A JP 2006002087A JP 2004181593 A JP2004181593 A JP 2004181593A JP 2004181593 A JP2004181593 A JP 2004181593A JP 2006002087 A JP2006002087 A JP 2006002087A
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- energy ray
- resin composition
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- 230000003287 optical effect Effects 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 239000007787 solid Substances 0.000 title abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 11
- -1 siloxane units Chemical group 0.000 claims description 35
- 125000003342 alkenyl group Chemical group 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 229920001971 elastomer Polymers 0.000 claims description 23
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims description 13
- 230000002745 absorbent Effects 0.000 claims description 12
- 239000002250 absorbent Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 230000000704 physical effect Effects 0.000 claims description 5
- 238000009864 tensile test Methods 0.000 claims description 4
- 125000005389 trialkylsiloxy group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000006096 absorbing agent Substances 0.000 abstract description 12
- 238000001723 curing Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 239000005060 rubber Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- YHHKOCQFUSUCCG-UHFFFAOYSA-N 3-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound OCC(C)C(=O)C1=CC=CC=C1 YHHKOCQFUSUCCG-UHFFFAOYSA-N 0.000 description 5
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 description 4
- 229960002130 benzoin Drugs 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000019382 gum benzoic Nutrition 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical class OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AMYKXJAXRJCLCV-UHFFFAOYSA-N (4-methylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(C)=CC=C1OC(=O)C1=CC=CC=C1O AMYKXJAXRJCLCV-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- OQZQDGSYKKFLTE-UHFFFAOYSA-N 1-(4-azidophenyl)-3-phenylprop-2-en-1-one Chemical compound C1=CC(N=[N+]=[N-])=CC=C1C(=O)C=CC1=CC=CC=C1 OQZQDGSYKKFLTE-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- VMCRQYHCDSXNLW-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2-dichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)Cl)C=C1 VMCRQYHCDSXNLW-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- YJQMXVDKXSQCDI-UHFFFAOYSA-N 2-ethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3SC2=C1 YJQMXVDKXSQCDI-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-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
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WRIACWNZRKYBDC-UHFFFAOYSA-N OC1=C(C=C(C=C1CCCC)CCCCCCCCCCC(=O)O)C1=CC=CC=2NN=NC21 Chemical compound OC1=C(C=C(C=C1CCCC)CCCCCCCCCCC(=O)O)C1=CC=CC=2NN=NC21 WRIACWNZRKYBDC-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl 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
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 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
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- TUKWPCXMNZAXLO-UHFFFAOYSA-N ethyl 2-nonylsulfanyl-4-oxo-1h-pyrimidine-6-carboxylate Chemical compound CCCCCCCCCSC1=NC(=O)C=C(C(=O)OCC)N1 TUKWPCXMNZAXLO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、優れたゴム物性を与える光学的立体造形用樹脂組成物に関する。 The present invention relates to a resin composition for optical three-dimensional modeling that gives excellent rubber properties.
近年、三次元ＣＡＤに入力されたデータに基づいて液状の光硬化性樹脂組成物を立体的に光学造形する方法が、金型などを作製することなく目的とする立体造形物を良好な寸法精度で製造し得ることから、広く採用されるようになっている。この方法については、特開昭５６−１４４４７８号公報（特許文献１）において、光硬化性樹脂に必要量の光エネルギーを供給することによって立体造形物を得る方法が開示され、更に特開昭６０−２４７５１５号公報（特許文献２）により基本的実用方法が提案された。その後、同様の技術又は改良された技術が、特開昭６２−３５９６６号公報（特許文献３）、特開平１−２０４９１５号公報（特許文献４）、特開平２−１１３９２５号公報（特許文献５）、特開平２−１４５６１６号公報（特許文献６）、特開平２−１５３７２２号公報（特許文献７）、特開平３−１５５２０号公報（特許文献８）、特開平３−２１４３２号公報（特許文献９）、特開平３−４１１２６号公報（特許文献１０）等に開示されている。 In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted. Regarding this method, Japanese Patent Laid-Open No. 56-144478 (Patent Document 1) discloses a method of obtaining a three-dimensional structure by supplying a required amount of light energy to a photocurable resin. No. 247515 (Patent Document 2) proposed a basic practical method. Thereafter, a similar or improved technique is disclosed in Japanese Patent Application Laid-Open No. 62-35966 (Patent Document 3), Japanese Patent Application Laid-Open No. 1-204915 (Patent Document 4), Japanese Patent Application Laid-Open No. 2-113925 (Patent Document 5). ), JP-A-2-145616 (Patent Document 6), JP-A-2-153722 (Patent Document 7), JP-A-3-15520 (Patent Document 8), JP-A-3-21432 (Patent Document) Document 9), Japanese Patent Laid-Open No. 3-41126 (Patent Document 10), and the like.
光学的立体造形法の代表的な例としては、容器に入れた液状光硬化性樹脂の液面に所望のパターンが得られるようにコンピューターで制御された紫外線レーザーを選択的に照射して所定厚みを硬化させ、次いで、該硬化層の上に１層分の液状樹脂を供給し、同様に紫外線レーザーで前記と同様に照射硬化させ、連続した硬化層を得る積層操作を繰り返すことによって最終的に立体造形物を得る方法を挙げることができる。この光学的立体造形方法は、形状のかなり複雑な造形物をも容易に、かつ比較的短時間に得ることができるため、近年特に注目を集めている。 As a typical example of the optical three-dimensional modeling method, a predetermined thickness is obtained by selectively irradiating an ultraviolet laser controlled by a computer so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. Finally, the liquid resin for one layer is supplied onto the cured layer, and similarly cured by irradiation with an ultraviolet laser in the same manner as described above, and finally the lamination operation for obtaining a continuous cured layer is repeated. The method of obtaining a three-dimensional molded item can be mentioned. This optical three-dimensional modeling method has attracted particular attention in recent years because a model with a fairly complicated shape can be obtained easily and in a relatively short time.
光学的造形などに用いる活性エネルギー線硬化性樹脂組成物に対しては、活性エネルギー線による硬化感度が高いこと、造形物の解像度がよく、造形精度に優れていること、硬化時の体積収縮率が小さいこと、硬化物の力学的特性が優れていること、自己接着性がよいこと、酸素雰囲気下での硬化特性がよいこと、低粘度であること、耐水性や耐湿性に優れており、経時的に水分や湿分の吸収が少なく、寸法安定性に優れていることなどの種々の特性が要求される。光造形等に用いられる樹脂組成物としては、従来、アクリレート系光硬化性樹脂組成物、ウレタンアクリレート系光硬化性樹脂組成物、エポキシ系光硬化性樹脂組成物、エポキシアクリレート系光硬化性樹脂組成物、ビニルエーテル系光硬化性樹脂組成物が知られている。 For active energy ray-curable resin compositions used for optical modeling, etc., the curing sensitivity by active energy rays is high, the resolution of the model is good, the modeling accuracy is excellent, and the volumetric shrinkage during curing Is small, excellent mechanical properties of the cured product, good self-adhesiveness, good curing properties in an oxygen atmosphere, low viscosity, excellent water resistance and moisture resistance, Various properties are required such as little absorption of moisture and moisture over time and excellent dimensional stability. Conventionally, as a resin composition used for optical modeling and the like, an acrylate photocurable resin composition, a urethane acrylate photocurable resin composition, an epoxy photocurable resin composition, and an epoxyacrylate photocurable resin composition And vinyl ether photocurable resin compositions are known.
近年、上述の光造形の技術を使って、「ゴムのような性状」、即ち応力の付与により破壊せずに容易に変形が起こり、応力を除くと元の形状に戻る性質を有する樹脂が求められている。
しかしながら、これらの樹脂を硬化せしめて得られる構造体は、基本的に剛性があり、ある程度以上の応力が付与されると破壊する性状を示すものである。
唯一、「ゴムのような性状」に近づけるため、ウレタンアクリレート系光硬化性樹脂組成物に柔軟成分を混合した系が「エラストマーライク（ゴムに似た性状）」と称されて上市されている（特許文献１１：特開平９−１６９８２７号公報参照）が、該樹脂の硬化物は、一般的なゴムのように柔らかい性状を示すものの、応力を解除しても元の形状には回復しない非弾性の性状であった。
In recent years, there has been a demand for a resin having the property of “rubber-like properties”, that is, easily deformed without breaking by applying stress, and returns to its original shape when stress is removed, using the above-mentioned stereolithography technology. It has been.
However, the structure obtained by curing these resins is basically rigid and exhibits a property of breaking when a certain level of stress is applied.
Only in order to bring it close to “rubber-like properties”, a system in which a flexible component is mixed with a urethane acrylate photocurable resin composition is called “elastomer-like (property similar to rubber)” and is now on the market ( Patent Document 11: Japanese Patent Laid-Open No. 9-169827), however, the cured product of the resin shows a soft property like general rubber, but does not recover to its original shape even when stress is released. It was the nature of.
一方、光硬化に関係なくゴム弾性を示す素材は数多く利用されている。例えば、エチレンプロピレンゴム、ブタジエンゴム、ポリウレタンゴム、シリコーンゴム、フッ素ゴムなどが代表的である。しかしながら、活性エネルギー線を照射することにより硬化して実用に耐え得る樹脂はシリコーンゴムに限定されていた。特に、紫外線硬化性オルガノポリシロキサンについては、かなりの実用例が開示されている（特許文献１２〜２２：特開平６−３２２２７２号公報、特開平７−２１６２３２号公報、特開平１１−１２５５６号公報、特開平１１−６０９５３号公報、特開平１１−２２８７０２号公報、特開２００２−３７１２６１号公報、特開２００３−２１３１３２号公報、特開平８−０５９８４３号公報、特開平８−２３１７３２号公報、特開平５−２２２１４３号公報、特開平７−２２８７８０号公報参照）。 On the other hand, many materials that exhibit rubber elasticity regardless of photocuring are used. For example, ethylene propylene rubber, butadiene rubber, polyurethane rubber, silicone rubber, fluorine rubber and the like are representative. However, a resin that can be cured and endured by irradiation with active energy rays is limited to silicone rubber. In particular, for UV-curable organopolysiloxanes, considerable practical examples have been disclosed (Patent Documents 12 to 22: JP-A-6-322272, JP-A-7-216232, JP-A-11-12556). JP-A-11-60953, JP-A-11-228702, JP-A-2002-371261, JP-A-2003-213132, JP-A-8-059843, JP-A-8-231732, (See Kaihei 5-222143 and JP-A-7-228780).
しかしながら、上述特許文献に挙げられた組成物でも、活性エネルギー線の照射により硬化はするものの、その硬化速度は光造形に適用するには依然遅く、実際の光造形に用いることはできなかった。また、たとえ時間を度外視して硬化せしめても、得られるゴム状モデルは、短時間で脆化しゴム弾性を示さなくなった。
このように、光造形が可能でゴム弾性を有する樹脂については何ら提案がないのが現状である。
However, even the compositions listed in the above-mentioned patent documents are cured by irradiation with active energy rays, but their curing rate is still slow to be applied to stereolithography and cannot be used for actual stereolithography. Moreover, even if the time was taken out and cured, the resulting rubbery model became brittle in a short time and did not show rubber elasticity.
As described above, there is no proposal for a resin that can be stereolithographically and has rubber elasticity.
本発明は、上記事情に鑑みなされたもので、エネルギー線照射以前には、保存安定性及び経時安定性に優れていて、高温下で長期間保存しても粘度の上昇が少なく、しかも光等の活性エネルギー線による硬化感度が高くて、光等の活性エネルギー線の照射により、寸法精度、造形精度、耐水性、耐湿性に優れ、長期間安定してゴム弾性を示し、特に力学的特性として１００％以上伸張後の弾性回復率が８０％以上のエラストマー物性を発現する硬化物を円滑に生産性よく製造することのできる活性エネルギー線硬化タイプの光学的立体造形用樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and is excellent in storage stability and temporal stability before irradiation with energy rays, has a small increase in viscosity even when stored at a high temperature for a long period of time, and has light, etc. It has a high curing sensitivity due to the active energy rays of the material, and by irradiation with active energy rays such as light, it has excellent dimensional accuracy, modeling accuracy, water resistance, moisture resistance, stable rubber elasticity for a long time, especially as a mechanical property To provide an active energy ray-curable resin composition for optical three-dimensional modeling, which can smoothly produce a cured product exhibiting elastomer properties having an elastic recovery rate of 80% or more after stretching by 100% or more. With the goal.
本発明者らは、上記目的を達成すべく鋭意検討を行い、まず光造形に適用可能なゴム特性を示す材質の探索から始めた。その結果、活性エネルギー線硬化型シリコーン組成物、特にアルケニル基含有オルガノポリシロキサン、メルカプト基含有オルガノポリシロキサン及び好ましくはこれらに加えてアルケニル基含有ＭＱレジンからなるシリコーンゴム（即ち、オルガノポリシロキサンエラストマー）系材料が光造形樹脂として有効であり、これに活性エネルギー線感受性重合開始剤、特にラジカル重合開始剤と、活性エネルギー線吸収剤とを配合することにより、その活性エネルギー線硬化性樹脂組成物の硬化物が、光造形のような活性エネルギー線を用いる成形加工等に円滑に用いることができ、活性エネルギー線による硬化感度に優れていて活性エネルギー線を照射したときに速やかに硬化させることができ、その一方で保存安定性や経時安定性に優れていて、長期間保存しても、特に高温下に長期間保存しても、粘度の上昇が少なく、光造形などに使用可能な流動状態を保持することのできる、取り扱い性に優れる活性エネルギー線硬化性シリコーン系樹脂組成物からなる光学的立体造形用樹脂組成物が得られることを見出した。 The inventors of the present invention have intensively studied to achieve the above object, and started by searching for a material exhibiting rubber characteristics applicable to stereolithography. As a result, an active energy ray-curable silicone composition, particularly an alkenyl group-containing organopolysiloxane, a mercapto group-containing organopolysiloxane, and preferably a silicone rubber comprising an alkenyl group-containing MQ resin in addition thereto (ie, organopolysiloxane elastomer) The system material is effective as an optical modeling resin, and by adding an active energy ray-sensitive polymerization initiator, particularly a radical polymerization initiator and an active energy ray absorber, to the active energy ray-curable resin composition. The cured product can be used smoothly for molding processing using active energy rays such as stereolithography, and it has excellent curing sensitivity with active energy rays and can be cured quickly when irradiated with active energy rays. On the other hand, it has excellent storage stability and stability over time Active energy ray curing with excellent handling properties that can maintain a fluid state that can be used for stereolithography, etc. It discovered that the resin composition for optical three-dimensional model | molding which consists of an adhesive silicone type resin composition was obtained.
更に、この樹脂組成物が、これに活性エネルギー線を照射して硬化した際には、解像度、造形精度、寸法精度、力学的特性、外観等に優れ、特に力学的特性については、従来の樹脂では達成することが不可能であった１００％以上伸張後の弾性回復率が少なくとも８０％以上のゴム弾性を発現する光硬化物（光造形物等）が得られることを見出した。 Furthermore, when this resin composition is cured by irradiating it with active energy rays, it is excellent in resolution, modeling accuracy, dimensional accuracy, mechanical properties, appearance, etc. Then, it was found that a photocured material (such as an optically shaped product) exhibiting rubber elasticity having an elastic recovery rate of at least 80% after stretching 100% or more, which could not be achieved, was obtained.
また、本発明者らは、造形直後にはゴム弾性を示すが、１ヶ月程度の時間経過後には造形物にクラックが容易に発生し、破断しやすくなる課題に遭遇し、該特定の化学末端構造の種類、特定の活性エネルギー線感受性ラジカル重合開始剤の含有量がゴム弾性を安定的に発現する課題解決因子であることを見出し、それらの種々の知見に基づいて本発明を完成した。 In addition, the present inventors show rubber elasticity immediately after modeling, but after a time of about one month, a crack is easily generated in the modeled object and encounters a problem that breaks easily, and the specific chemical end The present inventors have found that the type of structure and the content of a specific active energy ray-sensitive radical polymerization initiator are problem-solving factors that stably develop rubber elasticity, and have completed the present invention based on these various findings.
従って、本発明は、
（１）（Ｉ）活性エネルギー線硬化型シリコーン組成物、
（ＩＩ）活性エネルギー線感受性重合開始剤、
（ＩＩＩ）活性エネルギー線吸収剤
を含有してなることを特徴とする光学的立体造形用樹脂組成物、
（２）（Ｉ）成分の活性エネルギー線硬化型シリコーン組成物が、
（Ａ）アルケニル基含有オルガノポリシロキサン、及び
（Ｂ）メルカプト基含有オルガノポリシロキサン、
又は、
上記（Ａ），（Ｂ）成分、及び
（Ｃ）アルケニル基含有ＭＱレジン
からなるものである（１）記載の光学的立体造形用樹脂組成物、
（３）（Ｉ）成分の活性エネルギー線硬化型シリコーン組成物が、
（Ａ）下記一般式（１）
で示されるアルケニル基含有オルガノポリシロキサンと、
（Ｂ）下記一般式（２），（３）又は（４）
Ｒ3Ｏ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−Ｒ3 （２）
Ｒ1 3ＳｉＯ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−ＳｉＲ1 3 （３）
［ＹＳｉＯ3/2］x［Ｒ2 3ＳｉＯ1/2］y （４）
（但し、式（２），（３）は分子式であり、式（４）はシロキサン単位の比率を示す組成式である。式中、Ｒ1は上記の通り、Ｒ2は上記Ｒ1又はアルコキシ基、トリアルキルシリルオキシ基もしくはヒドロキシ基、Ｒ3はＲ1又は水素原子である。Ｙは炭素数１〜８のメルカプト基含有１価有機基である。ｘは３以上、ｙは０以上の数である。）
で示されるメルカプト基含有オルガノポリシロキサンと
を質量比（Ａ）／（Ｂ）＝５０／５０〜９８／２で含有すると共に、
（Ｃ）Ｒ1 3ＳｉＯ0.5単位、Ｒ1 (3-a)ＸaＳｉＯ0.5単位（但し、Ｒ1、Ｘ、ａは上記の通り）及びＳｉＯ2単位を含有し、（Ｒ1 3ＳｉＯ0.5＋Ｒ1 (3-a)ＸaＳｉＯ0.5）／ＳｉＯ2のモル比が０．６〜１．７であるアルケニル基含有ＭＱレジンを上記（Ａ），（Ｂ）成分の合計量と（Ｃ）成分の量との配合比（質量比）が１００／２００〜１００／１０となるように含有してなる（２）記載の光学的立体造形用樹脂組成物、
（４）活性エネルギー線感受性重合開始剤が、活性エネルギー線感受性ラジカル重合開始剤であり、（Ｉ）成分１００質量部に対し０．１〜５質量部配合されたものである（１），（２）又は（３）記載の光学的立体造形用樹脂組成物、
（５）活性エネルギー線吸収剤の含有量が、（Ｉ）成分１００質量部に対し０．００１〜０．５質量部である（１）〜（４）のいずれかに記載の光学的立体造形用樹脂組成物、
（６）硬化物の１００％以上伸張後の弾性回復率が８０％以上のエラストマー物性を１ヶ月以上保持する（１）〜（５）のいずれかに記載の光学的立体造形用樹脂組成物
を提供する。
Therefore, the present invention
(1) (I) an active energy ray-curable silicone composition,
(II) an active energy ray-sensitive polymerization initiator,
(III) A resin composition for optical three-dimensional modeling characterized by containing an active energy ray absorbent,
(2) The active energy ray-curable silicone composition of component (I) is
(A) an alkenyl group-containing organopolysiloxane, and (B) a mercapto group-containing organopolysiloxane,
Or
(A) The resin composition for optical three-dimensional model | molding of (1) description which consists of (A) and (B) component, and (C) alkenyl group containing MQ resin,
(3) The active energy ray-curable silicone composition of component (I)
(A) The following general formula (1)
An alkenyl group-containing organopolysiloxane represented by:
(B) The following general formula (2), (3) or (4)
R 3 O— (R 2 YSiO) x — (R 2 2 SiO) y —R 3 (2)
R 1 3 SiO— (R 2 YSiO) x — (R 2 2 SiO) y —SiR 1 3 (3)
[YSiO 3/2 ] x [R 2 3 SiO 1/2 ] y (4)
(However, the formulas (2) and (3) are molecular formulas, and the formula (4) is a composition formula showing the ratio of siloxane units. In the formula, R 1 is as described above, and R 2 is the above R 1 or alkoxy. A group, a trialkylsilyloxy group or a hydroxy group, R 3 is R 1 or a hydrogen atom, Y is a mercapto group-containing monovalent organic group having 1 to 8 carbon atoms, x is 3 or more, and y is 0 or more. Number.)
And a mercapto group-containing organopolysiloxane represented by the formula (A) / (B) = 50/50 to 98/2,
(C) R 1 3 SiO 0.5 unit, R 1 (3-a) X a SiO 0.5 unit (provided that R 1 , X and a are as described above) and SiO 2 unit (R 1 3 SiO 0.5 unit) An alkenyl group-containing MQ resin having a molar ratio of + R 1 (3-a) X a SiO 0.5 ) / SiO 2 of 0.6 to 1.7 and the total amount of the above components (A) and (B) and (C) The resin composition for optical three-dimensional modeling according to (2), which is contained so that the blending ratio (mass ratio) with the amount of components is 100/200 to 100/10,
(4) The active energy ray-sensitive polymerization initiator is an active energy ray-sensitive radical polymerization initiator, and is blended in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the component (1), ( 2) or the resin composition for optical three-dimensional modeling according to (3),
(5) Optical three-dimensional modeling in any one of (1)-(4) whose content of an active energy ray absorber is 0.001-0.5 mass part with respect to 100 mass parts of (I) component. Resin composition,
(6) The resin composition for optical three-dimensional modeling according to any one of (1) to (5), which retains elastomer physical properties of an elastic recovery rate of 80% or more after stretching 100% or more of the cured product for 1 month or more. provide.
本発明の光学的立体造形用樹脂組成物は、高温下で保存しても粘度の上昇が少なく、流動性を保持していて、光造形などのような活性エネルギー線を用いる造形や成形加工等に円滑に用いることができる。更に、活性エネルギー線を照射して硬化した際に、解像度、造形精度、寸法精度、力学的特性、外観等に優れる光硬化物（光造形物等）を形成する。特に力学的特性については、従来の樹脂では達成することの不可能であった少なくとも１ヶ月以上安定的に１００％以上伸張後の弾性回復率が８０％以上（即ち、８０〜１００％）、好ましくは９０％以上（９０〜１００％）、より好ましくは９５％以上（９５〜１００％）のエラストマー物性を発現する。 The resin composition for optical three-dimensional modeling of the present invention has little increase in viscosity even when stored at a high temperature, retains fluidity, and modeling or molding using active energy rays such as optical modeling Can be used smoothly. Furthermore, when it hardens | cures by irradiating an active energy ray, the photocured material (optical modeling thing etc.) which is excellent in the resolution, modeling precision, dimensional accuracy, mechanical characteristics, external appearance, etc. is formed. Especially regarding the mechanical properties, the elastic recovery after stretching 100% or more stably for at least one month, which was impossible to achieve with conventional resins, is 80% or more (ie 80 to 100%), preferably Exhibits an elastomer physical property of 90% or more (90 to 100%), more preferably 95% or more (95 to 100%).
本発明の光学的立体造形用樹脂組成物は、
（Ｉ）活性エネルギー線硬化型シリコーン組成物、
（ＩＩ）活性エネルギー線感受性重合開始剤、
（ＩＩＩ）活性エネルギー線吸収剤
を含有する。
The resin composition for optical three-dimensional modeling of the present invention is
(I) an active energy ray-curable silicone composition,
(II) an active energy ray-sensitive polymerization initiator,
(III) Contains an active energy ray absorbent.
この場合、（Ｉ）成分の活性エネルギー線硬化型シリコーン組成物は、
（Ａ）アルケニル基含有オルガノポリシロキサン、
（Ｂ）メルカプト基含有オルガノポリシロキサン、及び
必要により
（Ｃ）アルケニル基含有ＭＱレジン
からなり、活性エネルギー線により架橋してシリコーンゴム（即ち、オルガノポリシロキサンエラストマー）硬化物を与えるものである。
In this case, the active energy ray-curable silicone composition of component (I) is
(A) an alkenyl group-containing organopolysiloxane,
It consists of (B) a mercapto group-containing organopolysiloxane and, if necessary, (C) an alkenyl group-containing MQ resin, and is crosslinked by active energy rays to give a cured product of silicone rubber (ie, organopolysiloxane elastomer).
上記（Ａ）成分のアルケニル基含有オルガノポリシロキサンは、線状のもの（即ち、主鎖がジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖された直鎖状ジオルガノポリシロキサン）が好ましい。（Ａ）成分中のアルケニル基は、ケイ素原子に直接結合していてもよく、また、エーテル結合、エステル結合を含有し得る２価炭化水素基を介してケイ素原子に結合していてもよい。またこのアルケニル基は分子鎖末端のケイ素原子に結合したものであっても、分子鎖途中（分子鎖非末端）のケイ素原子に結合したものであってもよく、あるいは両者に結合したものであってもよいが、得られる硬化物の物理特性等の点から、少なくとも分子鎖（両）末端のケイ素原子に結合したアルケニル基を含有するものが好ましい。（Ａ）成分中のアルケニル基は、１分子中に少なくとも１個、好ましくは２個以上（通常、２〜２０個程度）存在することが必要である。このような（Ａ）成分としては、特に下記一般式（１）で表されるものが好ましい。 The alkenyl group-containing organopolysiloxane of the component (A) is linear (that is, a linear disilane having a main chain composed of repeating diorganosiloxane units and having both ends of the molecular chain blocked with triorganosiloxy groups. Organopolysiloxane) is preferred. The alkenyl group in component (A) may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a divalent hydrocarbon group that may contain an ether bond or an ester bond. The alkenyl group may be bonded to the silicon atom at the molecular chain end, bonded to the silicon atom in the middle of the molecular chain (non-terminal molecular chain), or bonded to both. However, from the viewpoint of physical properties of the cured product to be obtained, those containing at least an alkenyl group bonded to a silicon atom at the molecular chain (both) terminals are preferred. The alkenyl group in component (A) must be at least 1, preferably 2 or more (usually about 2 to 20) in one molecule. As such a component (A), those represented by the following general formula (1) are particularly preferable.
この場合、Ｒ1の非置換又は置換の１価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｔｅｒｔ−ブチル基、ブチル基などのアルキル基、シクロヘキシル基などのシクロアルキル基、フェニル基、トリル基などのアリール基、ベンジル基等のアラルキル基、又はこれらの基の炭素原子に結合している水素原子の１部又は全部をハロゲン原子、ヒドロキシ基、シアノ基などで置換した３，３，３−トリフロロプロピル基、ヒドロキシプロピル基、シアノエチル基などが挙げられる。この中ではメチル基、フェニル基が特に好ましい。更に、全てのＲ1の５０モル％以上がメチル基であり、１〜２０モル％がフェニル基であることが好ましい。Ｘはアルケニル基含有１価の有機基であり、炭素数２〜１２のものが好ましく、エーテル結合（−Ｏ−）又はエステル結合（−Ｃ（＝Ｏ）−Ｏ−）を介在していてもよいアルケニル基が挙げられ、これを例示すれば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ヘキセニル基、オクテニル基、（メタ）アクリロイルオキシプロピル基、（メタ）アクリロイルオキシエチル基、（メタ）アクリロイルオキシメチル基、シクロへキセニルエチル基、ビニルオキシプロピル基などが挙げられる。このアルケニル基含有１価有機基の量は、ＸとＲ1との合計量の０．００１〜１０モル％、特に０．０１〜５モル％であることが好ましい。 In this case, the unsubstituted or substituted monovalent hydrocarbon group for R 1 includes an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and a butyl group, and a cyclohexyl group. An aryl group such as a cycloalkyl group, a phenyl group or a tolyl group, an aralkyl group such as a benzyl group, or a part or all of the hydrogen atoms bonded to the carbon atoms of these groups is a halogen atom, a hydroxy group, a cyano group, etc. 3,3,3-trifluoropropyl group, hydroxypropyl group, cyanoethyl group and the like substituted with Among these, a methyl group and a phenyl group are particularly preferable. Furthermore, it is preferable that 50 mol% or more of all R 1 is a methyl group and 1 to 20 mol% is a phenyl group. X is an alkenyl group-containing monovalent organic group, preferably having 2 to 12 carbon atoms, and having an ether bond (—O—) or an ester bond (—C (═O) —O—) interposed therebetween. Examples thereof include vinyl, allyl, propenyl, isopropenyl, hexenyl, octenyl, (meth) acryloyloxypropyl, (meth) acryloyloxyethyl, (meth) ) An acryloyloxymethyl group, a cyclohexenylethyl group, a vinyloxypropyl group, etc. are mentioned. The amount of the alkenyl group-containing monovalent organic group, the total amount of 0.001 to 10 mole percent of the X and R 1, is preferably in particular 0.01 to 5 mol%.
本発明における（Ａ）成分のオルガノポリシロキサンの性状はオイル状又は生ゴム状である。その粘度は２５℃において、５０ｍＰａ・ｓ以上、特に１００ｍＰａ・ｓ以上が好ましい。この粘度の上限は特にないが、３０質量％のトルエン溶液としたときの粘度が、５０，０００ｍＰａ・ｓ以下であることが好ましい。
（Ａ）成分のオルガノポリシロキサンは、これらの分子構造を有する単一の重合体、これらの分子構造からなる共重合体、またこれらの重合体及び／又は共重合体の混合物である。
なお、（Ａ）成分は２種以上を併用してもよい。
The property of the organopolysiloxane of component (A) in the present invention is oily or raw rubbery. The viscosity at 25 ° C. is preferably 50 mPa · s or more, particularly preferably 100 mPa · s or more. The upper limit of the viscosity is not particularly limited, but the viscosity when a 30% by mass toluene solution is used is preferably 50,000 mPa · s or less.
The (A) component organopolysiloxane is a single polymer having these molecular structures, a copolymer comprising these molecular structures, or a mixture of these polymers and / or copolymers.
In addition, (A) component may use 2 or more types together.
次に、本発明における（Ｂ）成分のメルカプト基含有オルガノポリシロキサンは下記一般式（２），（３）又は（４）で示されるものが好ましい。但し、式（２），（３）は分子式であり、式（４）はシロキサン単位の比率を示す組成式である。
Ｒ3Ｏ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−Ｒ3 （２）
Ｒ1 3ＳｉＯ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−ＳｉＲ1 3 （３）
［ＹＳｉＯ3/2］x［Ｒ2 3ＳｉＯ1/2］y （４）
（式中、Ｒ1は上記の通り、Ｒ2は上記Ｒ1又はアルコキシ基、トリアルキルシリルオキシ基もしくはヒドロキシ基、Ｒ3はＲ1又は水素原子である。Ｙは炭素数１〜８のメルカプト基含有１価有機基である。ｘは３以上、ｙは０以上の数である。）
Next, the mercapto group-containing organopolysiloxane of the component (B) in the present invention is preferably one represented by the following general formula (2), (3) or (4). However, Formula (2) and (3) are molecular formulas, and Formula (4) is a compositional formula which shows the ratio of a siloxane unit.
R 3 O— (R 2 YSiO) x — (R 2 2 SiO) y —R 3 (2)
R 1 3 SiO— (R 2 YSiO) x — (R 2 2 SiO) y —SiR 1 3 (3)
[YSiO 3/2 ] x [R 2 3 SiO 1/2 ] y (4)
(Wherein R 1 is as described above, R 2 is R 1 or an alkoxy group, a trialkylsilyloxy group or a hydroxy group, R 3 is R 1 or a hydrogen atom. Y is a mercapto having 1 to 8 carbon atoms. A group-containing monovalent organic group, where x is 3 or more and y is 0 or more.)
上記式において、Ｒ2のアルコキシ基は炭素数１〜４のものが好ましく、トリアルキルシリルオキシ基の各アルキル基は炭素数１〜６のものが好ましい。Ｒ2としては、上記Ｒ1で例示したものに加えて、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基、ｔｅｒｔ−ブトキシ基などのアルコキシ基、トリメチルシリルオキシ基などのトリアルキルシリルオキシ基、ヒドロキシ基が挙げられるが、このうちメチル基、フェニル基、メトキシ基、トリメチルシリルオキシ基が好ましい。Ｙは炭素数１〜８のメルカプト基含有１価の有機基で、これを例示すると、２−メルカプトエチル基、３−メルカプトプロピル基、４−メルカプトブチル基、ｏ−メルカプトフェニル基、ｍ−メルカプトフェニル基、ｐ−メルカプトフェニル基等のメルカプト基含有アルキル基、メルカプト基含有アリール基などである。 In the above formula, the alkoxy group of R 2 preferably has 1 to 4 carbon atoms, and each alkyl group of the trialkylsilyloxy group preferably has 1 to 6 carbon atoms. R 2 includes, in addition to those exemplified for R 1 above, alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, and trimethylsilyloxy group. An alkylsilyloxy group and a hydroxy group are exemplified, and among them, a methyl group, a phenyl group, a methoxy group, and a trimethylsilyloxy group are preferable. Y is a C1-C8 mercapto group-containing monovalent organic group, and examples thereof include 2-mercaptoethyl group, 3-mercaptopropyl group, 4-mercaptobutyl group, o-mercaptophenyl group, m-mercapto. These include a mercapto group-containing alkyl group such as a phenyl group and a p-mercaptophenyl group, and a mercapto group-containing aryl group.
この場合、Ｙの含有量は、分子中のケイ素原子数に対して２０モル％以上（即ち２０〜１００モル％）、特に３０〜９０モル％、更には４０〜８０モル％であることが好ましい。
また、ｘは好ましくは３〜５０、特に好ましくは４〜２０であり、ｙは好ましくは０〜５０、特に好ましくは０〜２０であり、この（Ｂ）成分の粘度は１０〜１，０００ｍＰａ・ｓ程度であることが好ましい。
（Ｂ）成分のメルカプト基含有オルガノポリシロキサンは、例えば、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有２官能性及び／又は３官能性アルコキシシランを、必要に応じてジメチルジメトキシシラン、トリメチルメトキシシラン等の２官能性及び／又は１官能性アルキルアルコキシシランの共存下に（共）加水分解縮合することにより得ることができる。
なお、（Ｂ）成分のメルカプト基含有オルガノポリシロキサンは２種以上を併用してもよい。
In this case, the content of Y is preferably 20 mol% or more (that is, 20 to 100 mol%), particularly 30 to 90 mol%, more preferably 40 to 80 mol%, based on the number of silicon atoms in the molecule. .
X is preferably 3 to 50, particularly preferably 4 to 20, and y is preferably 0 to 50, particularly preferably 0 to 20. The viscosity of the component (B) is 10 to 1,000 mPa · s. It is preferably about s.
The (B) component mercapto group-containing organopolysiloxane requires, for example, a mercapto group-containing bifunctional and / or trifunctional alkoxysilane such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane. Accordingly, it can be obtained by (co) hydrolysis condensation in the presence of a bifunctional and / or monofunctional alkylalkoxysilane such as dimethyldimethoxysilane or trimethylmethoxysilane.
The mercapto group-containing organopolysiloxane (B) may be used in combination of two or more.
本発明の組成物の主たる硬化反応（架橋反応）は、（Ａ）成分中のアルケニル基と（Ｂ）成分中のメルカプト基とのラジカル付加反応によるが、両成分の質量比（Ａ）／（Ｂ）は５０／５０〜９８／２が好ましく、より好ましくは７０／３０〜９５／５である。９８／２を超えると硬化性が不十分となり、５０／５０未満であると十分な物性の造形物が得られなくなる場合がある。 The main curing reaction (crosslinking reaction) of the composition of the present invention is based on the radical addition reaction between the alkenyl group in the component (A) and the mercapto group in the component (B), but the mass ratio of both components (A) / ( B) is preferably 50/50 to 98/2, more preferably 70/30 to 95/5. If it exceeds 98/2, curability becomes insufficient, and if it is less than 50/50, a molded article having sufficient physical properties may not be obtained.
本発明のシリコーン組成物は、必要に応じて、（Ｃ）成分として、
Ｒ1 3ＳｉＯ0.5単位、Ｒ1 (3-a)ＸaＳｉＯ0.5単位（但し、Ｒ1、Ｘ、ａは上記の通り）及びＳｉＯ2単位を含有し、（Ｒ1 3ＳｉＯ0.5＋Ｒ1 (3-a)ＸaＳｉＯ0.5）／ＳｉＯ2のモル比が０．６〜１．７である三次元網状構造のオルガノポリシロキサン樹脂（ＭＱレジン）
を配合してもよい。なお、本発明において、ＭＱレジンとは、トリオルガノシロキシ単位（即ち、単官能性シロキサン単位）とＳｉＯ4/2単位とを必須に含有する、三次元網状構造のオルガノポリシロキサン樹脂を意味する。
（Ｒ1 3ＳｉＯ0.5＋Ｒ1 (3-a)ＸaＳｉＯ0.5）／ＳｉＯ2のモル比が０．６未満では造形性が低下することがあり、１．７を超えると保持力が低下することがある。また、（Ｃ）成分は２種以上併用してもよく、シラノール基をヒドロキシ基の質量として約１．５質量％以下含有してもよい。
The silicone composition of the present invention, as necessary, as component (C)
R 1 3 SiO 0.5 unit, R 1 (3-a) X a SiO 0.5 unit (provided that R 1 , X, and a are as described above) and SiO 2 unit, and (R 1 3 SiO 0.5 + R 1 ( 3-a) X a SiO 0.5 ) / SiO 2 molar ratio of the three-dimensional network structure is 0.6 to 1.7 organopolysiloxane resin (MQ resin)
May be blended. In the present invention, MQ resin means an organopolysiloxane resin having a three-dimensional network structure, which essentially contains a triorganosiloxy unit (that is, a monofunctional siloxane unit) and a SiO 4/2 unit.
If the molar ratio of (R 1 3 SiO 0.5 + R 1 (3-a) X a SiO 0.5 ) / SiO 2 is less than 0.6, the formability may be lowered, and if it exceeds 1.7, the holding power is lowered. Sometimes. Moreover, 2 or more types of (C) components may be used together and a silanol group may be contained about 1.5 mass% or less as a mass of a hydroxy group.
なお、Ｒ1 3ＳｉＯ0.5単位とＲ1 (3-a)ＸaＳｉＯ0.5単位の割合は、Ｒ1 (3-a)ＸaＳｉＯ0.5／（Ｒ1 3ＳｉＯ0.5＋Ｒ1 (3-a)ＸaＳｉＯ0.5）のモル比が０．０２〜０．３、特に０．０５〜０．２程度が好ましい。
また、（Ｃ）成分中のアルケニル基含有量は、０．３〜１０質量％、特に０．５〜５質量％程度が好ましい。
The ratio of R 1 3 SiO 0.5 unit to R 1 (3-a) X a SiO 0.5 unit is R 1 (3-a) X a SiO 0.5 / (R 1 3 SiO 0.5 + R 1 (3-a) The molar ratio of X a SiO 0.5 is preferably about 0.02 to 0.3, particularly about 0.05 to 0.2.
Further, the alkenyl group content in the component (C) is preferably about 0.3 to 10% by mass, particularly preferably about 0.5 to 5% by mass.
また、（Ａ），（Ｂ）成分の合計量と（Ｃ）成分の量との配合比（質量比）は１００／２００〜１００／１０が好ましく、より好ましくは１００／１００〜１００／４０である。１００／１０を超えるとゴムの強度が弱くなり、１００／２００未満であっても仕上がり粘度が高くなって使用できなくなる。 Further, the blending ratio (mass ratio) of the total amount of the components (A) and (B) and the amount of the component (C) is preferably 100/200 to 100/10, more preferably 100/100 to 100/40. is there. If it exceeds 100/10, the strength of the rubber becomes weak, and even if it is less than 100/200, the finished viscosity becomes high and the rubber cannot be used.
本発明においては、（Ａ）成分及び（Ｂ）成分、必要に応じて（Ｃ）成分を単に混合して組成物とするほか、（Ａ），（Ｃ）成分を両者の縮合反応物（シロキサンの平衡化反応物）として、これを（Ｂ）成分と混合してシリコーン組成物としてもよい。縮合反応はトルエンなどの溶剤に（Ａ），（Ｃ）成分を溶解させ、アルカリ性触媒を用いて、室温又は還流下に平衡化反応させる。 In the present invention, the (A) component and the (B) component, and if necessary, the (C) component is simply mixed to form a composition, and the (A) and (C) components are converted into a condensation reaction product (siloxane). (Equilibration reaction product) may be mixed with the component (B) to form a silicone composition. In the condensation reaction, the components (A) and (C) are dissolved in a solvent such as toluene, and an equilibration reaction is performed using an alkaline catalyst at room temperature or under reflux.
本発明の（ＩＩ）成分は、活性エネルギー線感受性重合開始剤であり、活性エネルギー線感受性ラジカル重合開始剤が好ましい。この場合、活性エネルギー線感受性ラジカル重合開始剤（以下、単に「ラジカル重合開始剤」ということがある）として、活性エネルギー線を照射したときにラジカル重合性有機化合物のラジカル重合を開始させ得る重合開始剤のいずれもが使用でき、例えば、ベンジル又はそのジアルキルアセタール系化合物、アセトフェノン系化合物、ベンゾイン又はそのアルキルエーテル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物などを挙げることができる。 The component (II) of the present invention is an active energy ray sensitive polymerization initiator, preferably an active energy ray sensitive radical polymerization initiator. In this case, as an active energy ray-sensitive radical polymerization initiator (hereinafter sometimes simply referred to as “radical polymerization initiator”), polymerization initiation that can initiate radical polymerization of a radical polymerizable organic compound when irradiated with active energy rays Any of the agents can be used, and examples thereof include benzyl or its dialkyl acetal compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone compound.
具体的には、ベンジル又はそのジアルキルアセタール系化合物としては、例えば、ベンジルジメチルケタール、ベンジル−β−メトキシエチルアセタール、１−ヒドロキシシクロヘキシルフェニルケトンなどを挙げることができる。また、アセトフェノン系化合物としては、例えば、アセトフェノン、４−メチルアセトフェノン、ジエトキシアセトフェノン、２−ヒドロキシメチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール（２，２−ジメトキシ−１，２−ジフェニル−エタン−１−オン）、２，２−ジエトキシ−１−フェニル−エタン−１−オン、４’−イソプロピル−２−ヒドロキシ−２−メチル−プロピオフェノン、２−ヒドロキシ−２−メチル−プロピオフェノン、ｐ−ジメチルアミノアセトフェノン、ｐ−ｔｅｒｔ−ブチルジクロロアセトフェノン、ｐ−ｔｅｒｔ−ブチルトリクロロアセトフェノン、ｐ−アジドベンザルアセトフェノンなどを挙げることができる。又はそのアルキルエーテルベンゾイン系化合物としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインノルマルブチルエーテル、ベンゾインイソブチルエーテルなどを挙げることができる。また、ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、ミヒラースケトン、４，４’−ビスジエチルアミノベンゾフェノン、４，４’−ジクロロベンゾフェノンなどを挙げることができる。チオキサントン系化合物としては、例えば、チオキサントン、２−メチルチオキサントン、２−エチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２−イソプロピルチオキサントンなどを挙げることができる。また、その他の化合物としてエチルアントラキノン、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サイドなどが例示される。 Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone, and the like. Examples of acetophenone compounds include acetophenone, 4-methylacetophenone, diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, benzyldimethyl ketal (2,2-dimethoxy-1,2-diphenyl). -Ethane-1-one), 2,2-diethoxy-1-phenyl-ethane-1-one, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl-pro Piophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like can be mentioned. Alternatively, examples of the alkyl ether benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and the like. Examples of other compounds include ethyl anthraquinone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
特に好ましい活性エネルギー線感受性ラジカル重合開始剤としては、常温で液体であり、（Ｉ）成分のシリコーン組成物中への良好な溶解性又は分散性、入手容易性などの点から２−ヒドロキシメチル−１−フェニルプロパン−１−オンが特に好ましく用いられる。また、本発明では、１種を単独で又は２種以上のラジカル重合開始剤を所望の性能に応じて配合して使用することができる。 Particularly preferred active energy ray-sensitive radical polymerization initiator is 2-hydroxymethyl-, which is liquid at room temperature and has good solubility or dispersibility in the silicone composition of component (I), availability, etc. 1-phenylpropan-1-one is particularly preferably used. Moreover, in this invention, 1 type can be used individually or in combination of 2 or more types of radical polymerization initiators according to desired performance.
本発明の活性エネルギー線感受性ラジカル重合開始剤の使用量は、（Ｉ）成分１００質量部に対して、０．１〜５質量部の割合で含有していることが好ましい。０．１質量部より少ないと十分な造形物が得られず、５質量部より多いと、得られた造形物が短時間で脆くなり、ゴム弾性を失い応力により容易に破壊されてしまい好ましくない。活性エネルギー線感受性ラジカル重合開始剤のより好ましい含有量は０．５〜５質量部、更に好ましい含有量は１〜５質量部である。 It is preferable that the usage-amount of the active energy ray sensitive radical polymerization initiator of this invention contains 0.1-5 mass parts with respect to 100 mass parts of (I) component. If the amount is less than 0.1 parts by mass, a sufficient shaped product cannot be obtained. If the amount is more than 5 parts by mass, the obtained shaped product becomes brittle in a short time, loses rubber elasticity, and is easily destroyed by stress. . The more preferable content of the active energy ray-sensitive radical polymerization initiator is 0.5 to 5 parts by mass, and the more preferable content is 1 to 5 parts by mass.
本発明の（ＩＩＩ）成分は、活性エネルギー線吸収剤であり、本発明で好ましく用いられる活性エネルギー線吸収剤の代表としては、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、サリチル酸フェニル系化合物及びシアノアクリレート系化合物を挙げることができ、本発明では光エネルギー吸収剤として、これらの化合物のうちの１種を単独で使用しても又は２種以上を併用してもよい。 The component (III) of the present invention is an active energy ray absorber, and representative examples of the active energy ray absorber preferably used in the present invention include benzotriazole compounds, benzophenone compounds, phenyl salicylate compounds, and cyanoacrylate compounds. In the present invention, as the light energy absorber, one of these compounds may be used alone, or two or more may be used in combination.
より具体的には、特許第３１１７３９４号公報に開示されている一般式（Ｉ），一般式（ＩＩ），一般式（ＩＩＩ）及び一般式（ＩＶ）に示されて挙げられている化合物が好ましい。即ち、一般式（Ｉ）は、
で表されるベンゾトリアゾール系化合物であり、一般式（ＩＩ）は、
で表されるベンゾフェノン系化合物であり、一般式（ＩＩＩ）は、
で表されるサリチル酸フェニル系化合物であり、一般式（ＩＶ）は、
で表されるシアノアクリレート系化合物である。
More specifically, compounds represented by the general formula (I), general formula (II), general formula (III) and general formula (IV) disclosed in Japanese Patent No. 3117394 are preferable. . That is, the general formula (I) is
Is a benzotriazole-based compound represented by general formula (II):
Is a benzophenone compound represented by general formula (III):
A phenyl salicylate compound represented by general formula (IV):
It is a cyanoacrylate type compound represented by these.
更には、２（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２［２’−ヒドロキシ−３’−ブチル−５’−（２”−カルボキシオクチル−エチル）フェニル］ベンゾトリアゾール、２−ヒドロキシ−４−メトキシベンゾフェノン、ｐ−メチルフェニルサリチレート、２−ヒドロキシ−４−オクチロキシベンゾフェノン、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール、｛ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ、Ｃ７−９側鎖及び直鎖アルキルエステル｝などが、高い活性エネルギー線吸収能、シリコーン系樹脂組成物中への良好な溶解性又は分散性、入手容易性などの点から特に好ましく用いられる。 Furthermore, 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 [2′-hydroxy-3′-butyl-5 ′-(2 ″ -carboxyoctyl-ethyl) phenyl] benzotriazole, 2- Hydroxy-4-methoxybenzophenone, p-methylphenyl salicylate, 2-hydroxy-4-octyloxybenzophenone, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) 5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) 5-chlorobenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, {benzene Propanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydride Xi, C7-9 side chain and straight chain alkyl ester} are particularly preferably used from the viewpoints of high active energy ray absorption ability, good solubility or dispersibility in the silicone resin composition, and availability. .
上記活性エネルギー線吸収剤の配合量は、（Ｉ）成分１００質量部に対し０．００１〜０．５質量部であることが好ましく、０．００５〜０．２５質量部であるのがより好ましく、０．０１〜０．１質量部であるのが更に好ましい。活性エネルギー線吸収剤の添加量が、０．００１質量部未満であると、本発明の目的が充分に達成されず、寸法精度、寸法安定性、力学的特性などに優れる立体造形物を得ることができなくなるおそれがある。一方、活性エネルギー線吸収剤の添加量が０．５質量部を超えると、光造形時の樹脂組成物の硬化速度が遅くなって造形速度の著しい低下をきたし、しかも得られる立体造形物の力学的特性が低くなり、実用上問題が生ずるおそれがある。また、活性エネルギー線吸収剤の添加量を（ＩＩ）成分の重合開始剤の含有量との関係でみると、重合開始剤の種類などに応じて異なるが、一般に、重合開始剤１質量部に対して活性エネルギー線吸収剤が０．００１〜０．２５質量部含まれるようにすると、光重合速度の低下などを招くことなく、寸法安定性、形状安定性、力学的特性などに優れる立体造形物を得ることができるので、好ましい。 The compounding amount of the active energy ray absorbent is preferably 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.25 parts by mass with respect to 100 parts by mass of the component (I). More preferably, the content is 0.01 to 0.1 parts by mass. When the addition amount of the active energy ray absorbent is less than 0.001 part by mass, the object of the present invention is not sufficiently achieved, and a three-dimensional molded article having excellent dimensional accuracy, dimensional stability, mechanical properties, and the like is obtained. There is a risk that it will not be possible. On the other hand, when the addition amount of the active energy ray absorbent exceeds 0.5 parts by mass, the curing rate of the resin composition during the optical modeling is slowed down, resulting in a significant decrease in the modeling rate. The physical characteristics may be lowered, which may cause problems in practical use. In addition, when the amount of the active energy ray absorbent is added in relation to the content of the polymerization initiator of the component (II), it varies depending on the kind of the polymerization initiator, but in general, the amount of the polymerization initiator is 1 part by mass. On the other hand, when the active energy ray absorbent is contained in an amount of 0.001 to 0.25 parts by mass, the three-dimensional modeling is excellent in dimensional stability, shape stability, mechanical properties, etc. without causing a decrease in the photopolymerization rate. Since a thing can be obtained, it is preferable.
活性エネルギー線硬化型シリコーン組成物中に活性エネルギー線吸収剤を上記の量で添加した本発明の光学的立体造形用樹脂組成物を用いると、硬化膜厚に対する光照射エネルギー量の許容範囲が拡大することにより、所望の厚み内でのエネルギー量のコントロールが従来よりも極めて簡単に、かつ円滑に行えるようになるため、寸法精度や寸法安定性に優れる立体造形物が得られるようになる。しかも、光化学的な反応率の向上も可能となり、それに伴って立体造形物の力学的特性などの向上をも図ることができる。そのような優れた効果が得られる理由は充分には明らかではないが、次のような理由によるものと考えられる。即ち、活性エネルギー線硬化型シリコーン組成物中に上記した所定量の活性エネルギー線吸収剤を添加することによって、活性エネルギー線吸収剤が活性エネルギー光線のエネルギーを一部吸収して主にＺ軸方向の光エネルギーの進入深度の調節及び均一化をもたらして光硬化層の厚さが均一になり、それと共に活性エネルギー線吸収剤に吸収された光エネルギーの一部が熱エネルギーに変換されてその熱エネルギーも樹脂の硬化に関与することによって、活性エネルギー線吸収剤を添加してあるにも拘わらず、樹脂の硬化速度の低減などが生じず、高い造形速度で立体造形物の製造を行っても寸法精度や寸法安定性などの特性に優れる高品質の立体造形物が形成されることによるものと推測される。 When the resin composition for optical three-dimensional modeling of the present invention in which the active energy ray absorbent is added in the above amount in the active energy ray curable silicone composition, the allowable range of the light irradiation energy amount with respect to the cured film thickness is expanded. By doing so, the amount of energy within a desired thickness can be controlled much more easily and smoothly than before, so that a three-dimensionally shaped object having excellent dimensional accuracy and dimensional stability can be obtained. In addition, it is possible to improve the photochemical reaction rate, and accordingly, it is possible to improve the mechanical properties of the three-dimensional structure. The reason why such an excellent effect is obtained is not sufficiently clear, but is considered to be due to the following reason. That is, by adding the predetermined amount of the active energy ray absorbent described above to the active energy ray curable silicone composition, the active energy ray absorber partially absorbs the energy of the active energy ray and mainly in the Z-axis direction. As a result, the thickness of the light-cured layer is made uniform by adjusting the depth of penetration of the light energy of the light, and at the same time, a part of the light energy absorbed by the active energy ray absorber is converted into heat energy, and the heat Even if the energy is also involved in the curing of the resin, even though the active energy ray absorber is added, there is no reduction in the curing rate of the resin, etc. It is presumed that this is due to the formation of a high-quality three-dimensional structure that is excellent in characteristics such as dimensional accuracy and dimensional stability.
本発明の光学的立体造形用樹脂組成物は、本発明の効果を損なわない限り、必要に応じてその他の成分を添加することができる。 The resin composition for optical three-dimensional model | molding of this invention can add another component as needed, unless the effect of this invention is impaired.
例えば、ジメチルポリシロキサン、ジメチルジフェニルポリシロキサンなどの非反応性のオルガノポリシロキサンを配合し得る。 For example, non-reactive organopolysiloxanes such as dimethylpolysiloxane and dimethyldiphenylpolysiloxane can be blended.
また、活性エネルギー線感受性ラジカル重合開始剤の存在下に活性エネルギー線を照射したときに重合反応及び／又は架橋反応を生ずる化合物として、（メタ）アクリレート系化合物、不飽和ポリエステル化合物、アリルウレタン系化合物、ポリチオール化合物等を配合し得る。これらのラジカル重合性有機化合物は単独で使用しても、又は２種以上を併用してもよい。 Further, as a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive radical polymerization initiator, (meth) acrylate compounds, unsaturated polyester compounds, allyl urethane compounds Polythiol compounds and the like can be blended. These radically polymerizable organic compounds may be used alone or in combination of two or more.
更に、粘度を下げるための溶剤として、トルエン、キシレンなどの芳香族系溶剤、ヘキサン、オクタン、イソパラフィンなどの脂肪族系溶剤、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、酢酸エチル、酢酸イソブチルなどのエステル系溶剤、ジイソプロピルエーテル、１，４−ジオキサンなどのエーテル系溶剤又はこれらの混合溶剤を配合することができる。 Furthermore, as solvents for lowering viscosity, aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, octane and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, isobutyl acetate and the like An ester solvent, an ether solvent such as diisopropyl ether, 1,4-dioxane, or a mixed solvent thereof can be blended.
硬化速度を促進するために、活性エネルギー線感受性ラジカル重合開始剤成分と併用するトリエチルアミン、ｐ−ジメチルアミノ安息香酸エチルエステル、Ｎ−メチルジエタノールアミンなどの反応促進剤を配合してもよい。 In order to accelerate the curing rate, a reaction accelerator such as triethylamine, p-dimethylaminobenzoic acid ethyl ester, N-methyldiethanolamine or the like used in combination with the active energy ray-sensitive radical polymerization initiator component may be blended.
また、顔料や染料等の着色剤、消泡剤、レベリング剤、増粘剤、難燃剤、酸化防止剤、充填剤（シリカ、ガラス粉、セラミックス粉、金属粉等）、改質用樹脂などの１種を単独で又は２種以上を適量含有していてもよい。 In addition, colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, antioxidants, fillers (silica, glass powder, ceramic powder, metal powder, etc.), modifying resins, etc. One kind may be contained alone or two or more kinds may be contained in appropriate amounts.
本発明の光学的立体造形用樹脂組成物は、室温（２５℃）で液状であることが好ましく、回転粘度計等による粘度測定において、０．１〜１００Ｐａ・ｓ、特に０．２〜５０Ｐａ・ｓ、とりわけ１〜３０Ｐａ・ｓであることが好ましい。 The resin composition for optical three-dimensional modeling of the present invention is preferably in a liquid state at room temperature (25 ° C.), and is 0.1 to 100 Pa · s, particularly 0.2 to 50 Pa · s in viscosity measurement using a rotational viscometer or the like. s, particularly 1 to 30 Pa · s is preferable.
本発明の光学的立体造形用樹脂組成物は、紫外線等の活性エネルギー線の照射により硬化し得る。この場合、照射量は、１〜５００ｍＪ／ｃｍ2、特に１０〜４００ｍＪ／ｃｍ2程度であることが好ましい。 The resin composition for optical three-dimensional model | molding of this invention can be hardened | cured by irradiation of active energy rays, such as an ultraviolet-ray. In this case, the irradiation amount is preferably about 1 to 500 mJ / cm 2 , particularly about 10 to 400 mJ / cm 2 .
また、活性エネルギー線の照射により硬化させた後、必要に応じてＵＶランプなどでポストキュアを行うことができる。 In addition, after curing by irradiation with active energy rays, post-curing can be performed with a UV lamp or the like, if necessary.
本発明の光学的立体造形用樹脂組成物を用いて光学的に立体造形を行うに当たっては、従来既知の光学的立体造形方法及び装置のいずれもが使用できる。好ましく採用され得る光学的立体造形法の代表例としては、液状をなす本発明の光学的立体造形用樹脂組成物に所望のパターンを有する硬化層が得られるように活性エネルギー線を選択的に照射して硬化層を形成し、次いでこの硬化層に未硬化の液状光学的立体造形用樹脂組成物を供給し、同様に活性エネルギー光線を照射して前記の硬化層と連続した硬化層を新たに形成する積層操作を繰り返すことによって最終的に目的とする立体的造形物を得る方法を挙げることができる。その際の活性エネルギー線としては、紫外線、電子線、Ｘ線、放射線、高周波などを挙げることができる。そのうちでも、３００〜４００ｎｍの波長を有する紫外線が経済的な観点から好ましく用いられ、その際の光源としては、紫外線レーザー（例えばＡｒレーザー、Ｈｅ−Ｃｄレーザー、半導体励起固体レーザーなど）、水銀ランプ、キセノンランプ、ハロゲンランプ、蛍光灯などを使用することができる。そのうちでも、レーザー光源及び水銀ランプが、エネルギーレベルを高めて造形時間を短縮でき、しかも集光性に優れていて高い造形精度を得ることができる点から、好ましく採用される。 Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern can be obtained in the liquid resin composition for optical three-dimensional modeling of the present invention. Then, a cured layer is formed, and then the uncured liquid optical three-dimensional resin composition is supplied to the cured layer, and similarly, the cured layer continuous with the cured layer is irradiated by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating the lamination | stacking operation to form. Examples of active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint, and as a light source at that time, an ultraviolet laser (for example, Ar laser, He-Cd laser, semiconductor excitation solid laser, etc.), mercury lamp, A xenon lamp, a halogen lamp, a fluorescent lamp, or the like can be used. Among these, a laser light source and a mercury lamp are preferably employed because they can increase the energy level and shorten the modeling time, and are excellent in light condensing properties and can achieve high modeling accuracy.
本発明の光学的立体造形用樹脂組成物を活性エネルギー照射により硬化せしめた硬化物は、引張り試験において少なくとも１００％以上の伸張が可能である。
引張り応力を解除した後には元の形状に戻り、伸張前の長さＬ０を伸長後の長さＬ１で除して１００分率で示した弾性回復率Ｌ０／Ｌ１が８０％以上（即ち、８０〜１００％）、好ましくは９０％以上（９０〜１００％）、更に好ましくは９５％以上（９５〜１００％）のエラストマー物性を発現する。
また、本発明の光学的立体造形用樹脂組成物を活性エネルギー照射により硬化せしめた後は、少なくとも１ヶ月以上、１００％以上伸張後の上記弾性回復率が８０％以上、好ましくは９０％以上、更に好ましくは９５％以上のエラストマー物性を継続して発現するのが大きな特徴である。
A cured product obtained by curing the resin composition for optical three-dimensional modeling of the present invention by irradiation with active energy can be stretched by at least 100% in a tensile test.
After releasing the tensile stress, it returns to its original shape, and the elastic recovery rate L0 / L1 expressed as 100 fractions by dividing the length L0 before stretching by the length L1 after stretching is 80% or more (that is, 80% To 100%), preferably 90% or more (90 to 100%), more preferably 95% or more (95 to 100%).
In addition, after the resin composition for optical three-dimensional modeling of the present invention is cured by irradiation with active energy, the elastic recovery rate after stretching at least 100% or more is 80% or more, preferably 90% or more, More preferably, it is a great feature that the elastomer properties of 95% or more are continuously developed.
本発明の光学的立体造形用樹脂組成物を光学的立体造形分野に用いる場合におけるその応用分野は特に制限されないが、代表的な応用分野としては、設計の途中で外観デザインを検証するためのモデル、部品の機能性をチェックするためのモデルなどを挙げることできる。 The application field in the case of using the resin composition for optical three-dimensional modeling of the present invention in the field of optical three-dimensional modeling is not particularly limited, but a typical application field is a model for verifying the appearance design during the design. And models for checking the functionality of parts.
特に、本発明の特徴であるゴム弾性を生かした機能チェックするモデルが可能となる。より具体的には、硬化した樹脂はシリコーンパッキンとしてそのまま用いることができる特性を有しているので、特殊な接合面を互いに有する接合体の間に挟むパッキン、人体の能動部位の動きに合わせてフィットするサポーター類やパット類、義足，義手などと人体との接合部材、補聴器のハウジングや、本来のＲＰ分野では自動車のタイヤのトレッドパターン開発、動力機械の稼働部、ロボットのフレキシブルな間接の保護カバー試作などの用途に有効に用いることができる。 In particular, a function check model that makes use of the rubber elasticity characteristic of the present invention is possible. More specifically, the cured resin has a characteristic that it can be used as it is as a silicone packing, so that the packing sandwiched between the joints having special joint surfaces between each other and the movement of the active part of the human body Fit supporters and pads, prosthetic legs, prosthetic joints and human body joints, hearing aid housings, in the original RP field, development of tread patterns for automobile tires, moving parts of power machines, flexible indirect protection of robots It can be used effectively for purposes such as cover prototyping.
なお、本発明の光学的立体造形用樹脂組成物は、光学的立体造形、光学的立体造形以外の活性エネルギー線を用いる成形、被覆材料、塗料などの各種用途にも用いることができる。 In addition, the resin composition for optical three-dimensional model | molding of this invention can be used also for various uses, such as shaping | molding which uses active energy rays other than optical three-dimensional model | mold, optical three-dimensional model | molding, a coating material, and a coating material.
以下、実施例と比較例を示し、本発明を具体的に説明するが、本発明は以下の実施例に制限されるものではない。なお、下記例において、部は質量部を意味する。また、Ｍｅはメチル基、Ｐｈはフェニル基、Ｖｉはビニル基を表す。
以下の例で得られた活性エネルギー線硬化物（試験片）の引張強度、引張伸度、引張弾性率はＪＩＳ Ｋ７１１３に準じて測定した。
また、以下の例で得られた活性エネルギー線硬化物（試験片）の弾性回復率及び経時後の弾性回復率の測定は、次のようにして測定した。
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to a following example. In addition, in the following example, a part means a mass part. Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.
The tensile strength, tensile elongation, and tensile elastic modulus of the active energy ray cured product (test piece) obtained in the following examples were measured according to JIS K7113.
Moreover, the measurement of the elastic recovery rate of the active energy ray cured material (test piece) obtained in the following examples and the elastic recovery rate after the elapse of time was measured as follows.
［弾性回復率測定試験］
ＪＩＳ Ｋ７１１３に準じた引っ張り試験測定用ダンベルと同じサンプルを用意し、上述の引っ張り試験で測定された伸度の値の９０％伸長（但し、伸度は１００％以上）を行った後、元に戻し、伸張前の長さＬ０を伸長後の長さＬ１で除して１００分率で示した。
同様にサンプルを造形して１ヶ月後、同様に試験を行い、「１ヶ月後の弾性回復率測定」を行った。
[Elastic recovery rate measurement test]
Prepare the same sample as the tensile test measurement dumbbell according to JIS K7113, and after extending 90% of the elongation value measured in the above tensile test (however, the elongation is 100% or more) The length L0 before stretching was divided by the length L1 after stretching and expressed as a percentage.
Similarly, one month after the sample was formed, the test was performed in the same manner, and “elastic recovery rate measurement after one month” was performed.
［実施例１］
（１）下記式で表されるアルケニル基含有オルガノポリシロキサン７０部、
（３）下記式で示されるメルカプト基含有オルガノポリシロキサン８部、
（５）活性エネルギー線吸収剤として；｛ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ、Ｃ７−９側鎖及び直鎖アルキルエステル｝と１−メトキシ−２−プロピルアセタートとの質量比９５／５の混合物「ＴＩＮＵＶＩＮ ３８４−２（商品名、チバ・スペシャリティ・ケミカルズ（株）製）」０．０５部。
[Example 1]
(1) 70 parts of an alkenyl group-containing organopolysiloxane represented by the following formula:
(3) 8 parts of a mercapto group-containing organopolysiloxane represented by the following formula:
(5) As an active energy ray absorber; {benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight chain Chain alkyl ester} and 1-methoxy-2-propyl acetate in a mass ratio of 95/5 “TINUVIN 384-2 (trade name, manufactured by Ciba Specialty Chemicals)” 0.05 part.
上記（１）〜（５）成分について、（１），（２）成分の混合物と（３）成分を混合し、次いで、これに（４），（５）成分を添加し、均一に混合し、光学的立体造形用樹脂組成物を製造した。 Regarding the above components (1) to (5), the mixture of the components (1) and (2) and the component (3) are mixed, and then the components (4) and (5) are added and mixed uniformly. The resin composition for optical three-dimensional modeling was manufactured.
得られた光学的立体造形用樹脂組成物を用いて、超高速光造形システム（帝人製機（株）製「ＳＯＬＩＦＯＲＭ５００Ｃ」）を使用して、半導体励起固体レーザー（出力１７５ｍＷ；波長３５５ｎｍ）で、照射エネルギー２０〜３０ｍＪ／ｃｍ2の条件下に、スライスピッチ（積層厚み）０．１０ｍｍ、１層当たりの平均造形時間２分で光学的立体造形を行って、ＪＩＳ Ｋ７１１３に準拠したダンベル状試験片を作製した。 Using the obtained resin composition for optical three-dimensional modeling, using an ultra-high-speed optical modeling system (“SOLIFORM 500C” manufactured by Teijin Seiki Co., Ltd.), with a semiconductor-excited solid laser (output 175 mW; wavelength 355 nm), Dumbbell-shaped test piece in accordance with JIS K7113 by performing optical three-dimensional modeling under an irradiation energy of 20 to 30 mJ / cm 2 with a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer. Was made.
得られた試験片を目視により観察したところ、歪みの全くない形状の良好な造形物であった。この試験片［立体造形物（硬化物）］を前記の光造形システムから取り出して、付着している未硬化物をｎ−ヘキサンで洗浄除去し、立体造形物を３ＫＷ紫外線ランプを用いて１０分間ポストキュアを行った。 When the obtained test piece was visually observed, it was a good shaped article having no distortion at all. This test piece [three-dimensional model (cured product)] is taken out from the optical modeling system, the uncured material adhering thereto is washed and removed with n-hexane, and the three-dimensional model is used for 10 minutes using a 3 KW ultraviolet lamp. Post cure was performed.
得られた試験片の引っ張り特性（引張強度、引張伸度及び引張弾性率）をＪＩＳ Ｋ７１１３に準じて測定したところ、下記の表１に示す通りであった。更に、上で得られた試験片の表面硬度（ショアＡ硬度）をＪＩＳ Ｋ６２５３のデュロメータ法により測定したところ、下記の表１に示す通りであった。 When the tensile properties (tensile strength, tensile elongation, and tensile modulus) of the obtained test piece were measured according to JIS K7113, they were as shown in Table 1 below. Furthermore, when the surface hardness (Shore A hardness) of the test piece obtained above was measured by the durometer method of JIS K6253, it was as shown in Table 1 below.
なお、造形に先立ち、硬化深度と照射エネルギーとの関係を調べた。ここで硬化深度の測定は次のようにして行った。 Prior to modeling, the relationship between curing depth and irradiation energy was examined. Here, the depth of cure was measured as follows.
硬化深度の測定法：硬化深度の測定は、“Ｒａｐｉｄ Ｐｒｏｔｏｔｙｐｉｎｇ ＆ Ｍａｎｕｆａｃｔｕｒｉｎｇ，Ｆｕｎｄａｍｅｎｔａｌｓ ｏｆ Ｓｔｅｒｅｏ Ｌｉｔｈｏｇｒａｐｈｙ”Ｐａｕｌ Ｆ．Ｊａｃｏｂｓ著，Ｓｏｃｉｅｔｙ ｏｆ Ｍａｎｕｆａｃｔｕｒｉｎｇ Ｅｎｇｉｎｅｅｒｓ，１９９２年に示された理論に基づいて測定した。露光量は描画スピードを変化することによりコントロールし、６〜１０種類のステップ状硬化物を作製した。この硬化物をピンセットで未硬化液中から取り出し、未硬化樹脂を取り除き、６〜１０種類の露光量に対する硬化膜厚を定圧ノギスで測定し、下記の図１に示した。また、硬化膜厚と露光量として与えられる照射エネルギーの自然対数の関係を図２に示した。図２で得られる直線は各樹脂特有の「硬化深度曲線」として呼ぶことができる。その勾配は「Ｄｐ」と称され、樹脂固有の光の透過深度であり、硬化深度曲線とｘ軸との交点、即ち硬化膜厚をゼロに外挿した照射エネルギー量は「Ｅｃ」臨界露光量と称される。Ｄｐ、Ｅｃ共に樹脂の固有の活性エネルギー線による硬化特性として把握することができる。得られた曲線から算出された値を表１に記載した。 Cure depth measurement method: The cure depth is measured by “Rapid Prototyping & Manufacturing, Fundamentals of Stereo Lithography”, Paul F. et al. Measurements were made based on the theory presented by Jacobs, Society of Manufacturing Engineers, 1992. The exposure amount was controlled by changing the drawing speed, and 6 to 10 types of step-like cured products were produced. The cured product was taken out of the uncured liquid with tweezers, the uncured resin was removed, and the cured film thickness for 6 to 10 types of exposure was measured with a constant pressure caliper, and is shown in FIG. 1 below. The relationship between the cured film thickness and the natural logarithm of the irradiation energy given as the exposure dose is shown in FIG. The straight line obtained in FIG. 2 can be referred to as a “curing depth curve” specific to each resin. The gradient is called “Dp”, which is the penetration depth of light inherent to the resin, and the intersection of the curing depth curve and the x-axis, that is, the irradiation energy amount extrapolated to the cured film thickness to zero is “Ec” critical exposure amount. It is called. Both Dp and Ec can be grasped as curing characteristics due to the intrinsic active energy rays of the resin. The values calculated from the obtained curves are shown in Table 1.
［実施例２］
（１）下記式で表されるアルケニル基含有オルガノポリシロキサン６０部、
（４）下記式で示されるメルカプト基含有オルガノポリシロキサン８部、
（６）活性エネルギー線吸収剤として；｛ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ、Ｃ７−９側鎖及び直鎖アルキルエステル｝と１−メトキシ−２−プロピルアセタートとの質量比９５／５の混合物「ＴＩＮＵＶＩＮ ３８４−２（商品名、チバ・スペシャルティ・ケミカルズ（株）製）」０．０５部。
[Example 2]
(1) 60 parts of an alkenyl group-containing organopolysiloxane represented by the following formula:
(4) 8 parts of a mercapto group-containing organopolysiloxane represented by the following formula:
(6) As an active energy ray absorber; {benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight chain Chain alkyl ester} and 1-methoxy-2-propyl acetate in a mass ratio of 95/5 “TINUVIN 384-2 (trade name, manufactured by Ciba Specialty Chemicals)” 0.05 part.
上記各（１）〜（６）成分について、（１），（２），（３）成分の混合物に（４）成分を混合し、次いで、これに（５），（６）成分を添加し、均一に混合し、光学的立体造形用樹脂組成物を製造した。 About each said (1)-(6) component, (4) component is mixed with the mixture of (1), (2), (3) component, and then (5), (6) component is added to this. Were mixed uniformly to produce a resin composition for optical three-dimensional modeling.
得られた光学的立体造形用樹脂組成物につき、実施例１と同様な手順で評価を行った。結果を下記表１及び図１，２に示した。 The obtained resin composition for optical three-dimensional modeling was evaluated in the same procedure as in Example 1. The results are shown in Table 1 below and FIGS.
［実施例３］
（１）下記式で表されるアルケニル基含有オルガノポリシロキサン７０部、
（３）下記式で示されるメルカプト基含有オルガノポリシロキサン１２部、
（５）活性エネルギー線吸収剤として；｛ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ、Ｃ７−９側鎖及び直鎖アルキルエステル｝と１−メトキシ−２−プロピルアセタートとの質量比９５／５の混合物「ＴＩＮＵＶＩＮ ３８４−２（商品名、チバ・スペシャルティ・ケミカルズ（株）製）」０．０５部。
[Example 3]
(1) 70 parts of an alkenyl group-containing organopolysiloxane represented by the following formula:
(3) 12 parts of a mercapto group-containing organopolysiloxane represented by the following formula:
(5) As an active energy ray absorber; {benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight chain Chain alkyl ester} and 1-methoxy-2-propyl acetate in a mass ratio of 95/5 “TINUVIN 384-2 (trade name, manufactured by Ciba Specialty Chemicals)” 0.05 part.
上記各（１）〜（５）成分について、（１），（２）成分の混合物に（３）成分を混合し、次いで、これに（４），（５）成分を添加し、均一に混合し、光学的立体造形用樹脂組成物を製造した。 About each said (1)-(5) component, (3) component is mixed with the mixture of (1), (2) component, and then (4), (5) component is added to this, and it mixes uniformly. And the resin composition for optical three-dimensional modeling was manufactured.
得られた光学的立体造形用樹脂組成物につき、実施例１と同様な手順で評価を行った。結果を表１及び図１，２に示した。 The obtained resin composition for optical three-dimensional modeling was evaluated in the same procedure as in Example 1. The results are shown in Table 1 and FIGS.
［比較例１］
（１）下記式で表されるアルケニル基含有オルガノポリシロキサン７０部、
（２）Ｍｅ3ＳｉＯ0.5単位、Ｍｅ2ＭＡＳｉＯ0.5単位、ＳｉＯ2単位からなり、［（Ｍｅ3ＳｉＯ0.5＋Ｍｅ2ＶｉＳｉＯ0.5）／ＳｉＯ2＝０．８（モル比）］である三次元網状構造のオルガノポリシロキサン樹脂（ビニル基含有量２質量％）３０部、
（３）活性エネルギー線感受性ラジカル開始剤として、２−ヒドロキシメチル−１−フェニルプロパン−１−オン；「ダロキュア１１７３（商品名、チバ・スペシャルティ・ケミカルズ（株）製）」２部、
（４）活性エネルギー線吸収剤として；｛ベンゼンプロパン酸、３−（２Ｈ−ベンゾトリアゾール−２−イル）−５−（１，１−ジメチルエチル）−４−ヒドロキシ、Ｃ７−９側鎖及び直鎖アルキルエステル｝と１−メトキシ−２−プロピルアセタートとの質量比９５／５の混合物「ＴＩＮＵＶＩＮ ３８４−２（商品名、チバ・スペシャルティ・ケミカルズ（株）製）」０．０５部。
[Comparative Example 1]
(1) 70 parts of an alkenyl group-containing organopolysiloxane represented by the following formula:
(2) A three-dimensional network structure consisting of Me 3 SiO 0.5 units, Me 2 MASiO 0.5 units, and SiO 2 units and having [(Me 3 SiO 0.5 + Me 2 ViSiO 0.5 ) / SiO 2 = 0.8 (molar ratio)]. 30 parts of an organopolysiloxane resin (vinyl group content 2% by mass),
(3) As an active energy ray-sensitive radical initiator, 2-hydroxymethyl-1-phenylpropan-1-one; “Darocur 1173 (trade name, manufactured by Ciba Specialty Chemicals)” 2 parts,
(4) As an active energy ray absorbent; {benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight chain Chain alkyl ester} and 1-methoxy-2-propyl acetate in a mass ratio of 95/5 “TINUVIN 384-2 (trade name, manufactured by Ciba Specialty Chemicals)” 0.05 part.
上記各成分について、（１）〜（４）成分を混合し、得られた光学的立体造形用樹脂組成物につき、実施例１と同様な手順で評価を行ったが、満足な造形物が得られなかった。 About each said component, (1)-(4) component was mixed, and it evaluated in the procedure similar to Example 1 about the obtained resin composition for optical three-dimensional model | molding, but a satisfying model | molding thing was obtained. I couldn't.
［比較例２］
活性エネルギー線感受性ラジカル開始剤を添加しないほかは、実施例１のシリコーン組成物と全く同じ組成のものを調製し、光学的立体造形用樹脂組成物を得た。
得られた光学的立体造形用樹脂組成物につき、実施例１と同様な手順で評価を行った。結果を表１及び図３，４に示した。図より硬化深度が照射エネルギーでコントロールできるものの、満足な造形物を得るには非常に大きなエネルギーが必要とされ、実際の光造形に用いることは困難であった。
[Comparative Example 2]
Except not adding an active energy ray sensitive radical initiator, the thing of the completely same composition as the silicone composition of Example 1 was prepared, and the resin composition for optical three-dimensional modeling was obtained.
The obtained resin composition for optical three-dimensional modeling was evaluated in the same procedure as in Example 1. The results are shown in Table 1 and FIGS. Although the curing depth can be controlled by irradiation energy as shown in the figure, a very large energy is required to obtain a satisfactory modeled object, and it is difficult to use it for actual optical modeling.
Claims (7)
（ＩＩ）活性エネルギー線感受性重合開始剤、
（ＩＩＩ）活性エネルギー線吸収剤
を含有してなることを特徴とする光学的立体造形用樹脂組成物。 (I) an active energy ray-curable silicone composition,
(II) an active energy ray-sensitive polymerization initiator,
(III) A resin composition for optical three-dimensional modeling comprising an active energy ray absorbent.
（Ａ）アルケニル基含有オルガノポリシロキサン、及び
（Ｂ）メルカプト基含有オルガノポリシロキサン、
又は、
上記（Ａ），（Ｂ）成分、及び
（Ｃ）アルケニル基含有ＭＱレジン
からなるものである請求項１記載の光学的立体造形用樹脂組成物。 The active energy ray-curable silicone composition of component (I)
(A) an alkenyl group-containing organopolysiloxane, and (B) a mercapto group-containing organopolysiloxane,
Or
The resin composition for optical three-dimensional modeling according to claim 1, comprising the (A) and (B) components, and (C) an alkenyl group-containing MQ resin.
（Ａ）下記一般式（１）
で示されるアルケニル基含有オルガノポリシロキサンと、
（Ｂ）下記一般式（２），（３）又は（４）
Ｒ3Ｏ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−Ｒ3 （２）
Ｒ1 3ＳｉＯ−（Ｒ2ＹＳｉＯ）x−（Ｒ2 2ＳｉＯ）y−ＳｉＲ1 3 （３）
［ＹＳｉＯ3/2］x［Ｒ2 3ＳｉＯ1/2］y （４）
（但し、式（２），（３）は分子式であり、式（４）はシロキサン単位の比率を示す組成式である。式中、Ｒ1は上記の通り、Ｒ2は上記Ｒ1又はアルコキシ基、トリアルキルシリルオキシ基もしくはヒドロキシ基、Ｒ3はＲ1又は水素原子である。Ｙは炭素数１〜８のメルカプト基含有１価有機基である。ｘは３以上、ｙは０以上の数である。）
で示されるメルカプト基含有オルガノポリシロキサンと
を質量比（Ａ）／（Ｂ）＝５０／５０〜９８／２で含有すると共に、
（Ｃ）Ｒ1 3ＳｉＯ0.5単位、Ｒ1 (3-a)ＸaＳｉＯ0.5単位（但し、Ｒ1、Ｘ、ａは上記の通り）及びＳｉＯ2単位を含有し、（Ｒ1 3ＳｉＯ0.5＋Ｒ1 (3-a)ＸaＳｉＯ0.5）／ＳｉＯ2のモル比が０．６〜１．７であるアルケニル基含有ＭＱレジンを上記（Ａ），（Ｂ）成分の合計量と（Ｃ）成分の量との配合比（質量比）が１００／２００〜１００／１０となるように含有してなる請求項２記載の光学的立体造形用樹脂組成物。 The active energy ray-curable silicone composition of component (I)
(A) The following general formula (1)
An alkenyl group-containing organopolysiloxane represented by:
(B) The following general formula (2), (3) or (4)
R 3 O— (R 2 YSiO) x — (R 2 2 SiO) y —R 3 (2)
R 1 3 SiO— (R 2 YSiO) x — (R 2 2 SiO) y —SiR 1 3 (3)
[YSiO 3/2 ] x [R 2 3 SiO 1/2 ] y (4)
(However, the formulas (2) and (3) are molecular formulas, and the formula (4) is a composition formula showing the ratio of siloxane units. In the formula, R 1 is as described above, and R 2 is the above R 1 or alkoxy. A group, a trialkylsilyloxy group or a hydroxy group, R 3 is R 1 or a hydrogen atom, Y is a mercapto group-containing monovalent organic group having 1 to 8 carbon atoms, x is 3 or more, and y is 0 or more. Number.)
And a mercapto group-containing organopolysiloxane represented by the formula (A) / (B) = 50/50 to 98/2,
(C) R 1 3 SiO 0.5 unit, R 1 (3-a) X a SiO 0.5 unit (provided that R 1 , X and a are as described above) and SiO 2 unit (R 1 3 SiO 0.5 unit) An alkenyl group-containing MQ resin having a molar ratio of + R 1 (3-a) X a SiO 0.5 ) / SiO 2 of 0.6 to 1.7 and the total amount of the above components (A) and (B) and (C) The resin composition for optical three-dimensional model | molding of Claim 2 formed so that a compounding ratio (mass ratio) with the quantity of a component may become 100 / 200-100 / 10.
7. For optical three-dimensional modeling according to any one of claims 1 to 6, wherein after being cured by irradiation with active energy, the elastic recovery rate after stretching 100% is at least one month or more and exhibits an elastomeric property of 80% or more. Resin composition.
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| JP2007291313A (en) * | 2005-07-28 | 2007-11-08 | Osaka City | Ultraviolet light curable resin composition, cured material of the same and various article derived from the same |
| WO2009119908A1 (en) | 2008-03-28 | 2009-10-01 | テルモ株式会社 | Three-dimensional model of body tissue and method of producing the same |
| WO2011136170A1 (en) * | 2010-04-26 | 2011-11-03 | 株式会社スリーボンド | Photocurable silicone gel composition and application thereof |
| CN110183665A (en) * | 2019-05-28 | 2019-08-30 | 安庆北化大科技园有限公司 | A kind of preparation method and applications of the resin of MTQ containing sulfydryl |
| WO2020026748A1 (en) | 2018-08-02 | 2020-02-06 | 信越化学工業株式会社 | Ultraviolet curable silicone composition for stereolithography and cured product of same |
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