KR102195639B1 - Composition for optical three-dimensional molding - Google Patents
Composition for optical three-dimensional molding Download PDFInfo
- Publication number
- KR102195639B1 KR102195639B1 KR1020150041372A KR20150041372A KR102195639B1 KR 102195639 B1 KR102195639 B1 KR 102195639B1 KR 1020150041372 A KR1020150041372 A KR 1020150041372A KR 20150041372 A KR20150041372 A KR 20150041372A KR 102195639 B1 KR102195639 B1 KR 102195639B1
- Authority
- KR
- South Korea
- Prior art keywords
- resin composition
- meth
- photocurable resin
- dimensional
- acrylate
- Prior art date
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- 238000000465 moulding Methods 0.000 title claims description 36
- 230000003287 optical effect Effects 0.000 title description 9
- 239000000203 mixture Substances 0.000 title description 3
- 239000011342 resin composition Substances 0.000 claims abstract description 85
- 238000007493 shaping process Methods 0.000 claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 34
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012952 cationic photoinitiator Substances 0.000 claims abstract description 23
- 125000002091 cationic group Chemical group 0.000 claims abstract description 14
- -1 oxetane compound Chemical class 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000004593 Epoxy Substances 0.000 claims description 26
- 229920005862 polyol Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 82
- 230000000052 comparative effect Effects 0.000 description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 13
- 238000001723 curing Methods 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- GBOJZXLCJZDBKO-UHFFFAOYSA-N 2-(2-chlorophenyl)-2-[2-(2-chlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC=C1C1(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=CC=CC=2)Cl)N=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=N1 GBOJZXLCJZDBKO-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 150000002314 glycerols Chemical class 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- KHKNFKNBERMAAR-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)N(CCO)C1=O KHKNFKNBERMAAR-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- YTZSKPAYFHSKOL-UHFFFAOYSA-N 2-(2,3-dichlorophenyl)-2-[2-(2,3-dichlorophenyl)-4,5-diphenylimidazol-2-yl]-4,5-diphenylimidazole Chemical compound ClC1=CC=CC(C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C2(N=C(C(=N2)C=2C=CC=CC=2)C=2C=CC=CC=2)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl YTZSKPAYFHSKOL-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 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
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 150000003445 sucroses Chemical class 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-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
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 description 1
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-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
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 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
- QIRUERQWPNHWRC-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-ylmethyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(CC=2C=C3OCOC3=CC=2)=N1 QIRUERQWPNHWRC-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- MCNPOZMLKGDJGP-QPJJXVBHSA-N 2-[(e)-2-(4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1\C=C\C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 MCNPOZMLKGDJGP-QPJJXVBHSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 1
- XOPKKHCDIAYUSK-UHFFFAOYSA-N 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound O1C(C)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XOPKKHCDIAYUSK-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Abstract
본 발명은 양이온 경화성 단량체, 양이온성 광개시제, (메타)아크릴계 단량체, 광라디칼 발생제, 액정형 고분자 및 가교제를 포함하는 입체 조형용 광경화성 수지 조성물에 관한 것으로, 상기 액정형 고분자 및 가교제를 포함함으로써, 입체 조형용 광경화성 수지 조성물의 기계적 강도 및 내열성을 향상시킬 수 있다.The present invention relates to a photocurable resin composition for stereoscopic shaping comprising a cationic curable monomer, a cationic photoinitiator, a (meth)acrylic monomer, a photoradical generator, a liquid crystal polymer, and a crosslinking agent, by including the liquid crystal polymer and a crosslinking agent, The mechanical strength and heat resistance of the photocurable resin composition for three-dimensional shaping can be improved.
Description
본 발명은 입체 조형용 광경화성 수지 조성물에 관한 것으로, 보다 자세하게는 양이온 경화성 단량체, 양이온성 광개시제, (메타)아크릴계 단량체, 광라디칼 발생제, 액정형 고분자 및 가교제를 포함하는 입체 조형용 광경화성 수지 조성물에 관한 것이다.The present invention relates to a photocurable resin composition for stereoscopic shaping, and more particularly, to a photocurable resin composition for stereoscopic shaping comprising a cationic curable monomer, a cationic photoinitiator, a (meth)acrylic monomer, a photoradical generator, a liquid crystal polymer, and a crosslinking agent. About.
최근, 삼차원 CAD에 입력된 데이터에 기초하여 액상의 광경화성 수지 조성물을 입체적으로 광학 조형하는 방법이, 금형 등을 제작하지 않고도 목적으로 하는 입체 조형물을 양호한 치수 정밀도로 제조할 수 있어 널리 채용되고 있다.Recently, a method of three-dimensionally optically shaping a liquid photocurable resin composition based on data input to a three-dimensional CAD has been widely adopted since it is possible to manufacture a three-dimensional object of interest with good dimensional accuracy without making a mold or the like. .
광학적 입체 조형법의 대표적인 예로는, 용기에 넣은 액상 광경화성 수지의 액면에 원하는 패턴이 얻어지도록 컴퓨터로 제어된 자외선 레이저를 선택적으로 조사하여 소정 두께를 경화시키고, 이어서 이 경화층 위에 1층분의 액상 수지를 공급하고, 마찬가지로 자외선 레이저로 상기와 같이 조사 경화시켜, 연속된 경화층을 얻는 적층 조작을 반복함으로써 최종적으로 입체 조형물을 얻는 방법을 들 수 있다. 이 광학적 입체 조형 방법은 형상이 상당히 복잡한 조형물도 비교적 단시간에 용이하게 얻을 수 있다.A representative example of the optical three-dimensional shaping method is to cure a predetermined thickness by selectively irradiating a computer-controlled ultraviolet laser to obtain a desired pattern on the liquid surface of a liquid photocurable resin placed in a container, and then to cure a layer of liquid on the cured layer. A method of finally obtaining a three-dimensional sculpture by supplying a resin and repeating the lamination operation to obtain a continuous cured layer by irradiating and curing it with an ultraviolet laser as described above is mentioned. This optical three-dimensional shaping method can easily obtain a sculpture having a fairly complex shape in a relatively short time.
광학적 입체 조형에 이용하는 수지 또는 수지 조성물의 조건으로는, 활성 에너지선에 의한 경화 감도가 높을 것, 저점도로 조형시의 취급성이 우수할 것, 경시적으로 수분이나 습기의 흡수가 적어 경화 감도의 저하가 없을 것, 조형물의 해상도가 높아 조형 정밀도가 우수할 것, 경화시의 체적 수축률이 작을 것, 경화하여 얻어지는 조형물이 역학적 특성, 내수성이나 내습성, 내열성 등이 우수할 것 등, 여러 특성이 요구된다.The conditions of the resin or resin composition used for optical three-dimensional shaping include high curing sensitivity by active energy rays, excellent handling during shaping with low viscosity, and less moisture or moisture absorption over time. Various properties such as no deterioration, high resolution of the sculpture, excellent molding accuracy, low volume shrinkage during curing, and excellent mechanical properties, water resistance, moisture resistance, heat resistance, etc. Required.
광학적 조형용의 수지 조성물로는 종래, 아크릴레이트계 광경화성 수지 조성물, 우레탄 아크릴레이트계 광경화성 수지 조성물, 에폭시계 광경화성 수지 조성물, 에폭시 아크릴레이트계 광경화성 수지 조성물 및 비닐에테르계 광경화성 수지 조성물이 제안되어 이용되어 왔다. 이들 중에서, 에폭시계 광경화성 수지 조성물은 치수 정밀도가 우수한 조형물을 형성할 수 있어 최근 주목 받고 있다.As resin compositions for optical shaping, conventionally, acrylate-based photocurable resin compositions, urethane acrylate-based photocurable resin compositions, epoxy-based photocurable resin compositions, epoxy acrylate-based photocurable resin compositions, and vinyl ether-based photocurable resin compositions It has been proposed and used. Among these, the epoxy-based photocurable resin composition has recently attracted attention because it can form a sculpture having excellent dimensional accuracy.
또한, 에폭시 화합물 등의 양이온 중합성 유기 화합물을 포함하는 광학적 입체 조형용 수지 조성물에 옥세탄 화합물을 배합하여 광경화 감도를 향상시키고, 그에 의해 조형 시간의 단축을 도모하는 것이 일본 특허공개 2004-217934호에 제안되어 있다.In addition, Japanese Patent Laid-Open No. 2004-217934 aims to shorten the molding time by blending an oxetane compound into a resin composition for optical three-dimensional molding containing a cationic polymerizable organic compound such as an epoxy compound to improve photocuring sensitivity and thereby shorten the molding time. Is proposed in
본 발명은 입체 조형용 광경화성 수지 조성물의 성분 중 하나로 슈퍼 엔지니어링 플라스틱(Super engineering plastic) 중 하나인 액정형 고분자(Liquid crystal polymer)를 사용함으로써, 경화시 입체 조형용 광경화성 수지의 감도 저하를 최소화시키며, 기계적 강도, 내열성 및 열변형 온도(Heat distortion temperature, HDT)를 증가시키는 것을 목적으로 한다.The present invention uses a liquid crystal polymer, which is one of super engineering plastics, as one of the components of the photocurable resin composition for three-dimensional molding, thereby minimizing the decrease in the sensitivity of the photocurable resin for three-dimensional molding during curing, It aims to increase the mechanical strength, heat resistance and heat distortion temperature (HDT).
또한, 본 발명은 입체 조형용 광경화성 수지 조성물의 성분 중 하나로 가교제(Cross-linker)를 사용함으로써, 입체 조형용 광경화성 수지 조성물의 경화밀도를 상승시켜, 기계적 강도, 내열성 및 열변형 온도를 증가시키는 것을 목적으로 한다.In addition, the present invention is to increase the curing density of the three-dimensional molding photocurable resin composition by using a cross-linker as one of the components of the three-dimensional molding photocurable resin composition, increasing the mechanical strength, heat resistance and heat distortion temperature. The purpose.
상기 목적을 달성하기 위하여,To achieve the above object,
본 발명은 양이온 경화성 단량체, 양이온성 광개시제, (메타)아크릴계 단량체, 광라디칼 발생제, 액정형 고분자 및 가교제를 포함하는 입체 조형용 광경화성 수지 조성물을 제공한다.The present invention provides a photocurable resin composition for stereoscopic shaping comprising a cationic curable monomer, a cationic photoinitiator, a (meth)acrylic monomer, a photoradical generator, a liquid crystal polymer, and a crosslinking agent.
본 발명의 입체 조형용 광경화성 수지 조성물은 액정형 고분자를 포함함으로써, 입체 조형용 광경화성 수지 조성물의 광경화시, 점도를 상승시키며, 감도를 최소화할 수 있으며, 기계적 강도 및 내열성을 향상시킬 수 있다.The photocurable resin composition for three-dimensional shaping of the present invention includes a liquid crystal polymer, so that when the photo-curable photo-curable resin composition for three-dimensional shaping is photocured, the viscosity may be increased, sensitivity may be minimized, and mechanical strength and heat resistance may be improved.
또한, 상기 액정형 고분자는 입자 형태이며, 상기 액정형 고분자의 비중과 액정형 고분자 이외의 입체 조형용 광경화성 수지 조성물 간의 비중이 비슷하여 입체 조형용 광경화성 수지 조성물 제조시 분산이 용이한 장점을 지니고 있다.In addition, the liquid crystal polymer is in the form of particles, and the specific gravity of the liquid crystal polymer and the specific gravity between the photocurable resin composition for three-dimensional shaping other than the liquid crystal polymer are similar, so that it has the advantage of being easy to disperse when preparing a three-dimensional shaping photocurable resin composition. .
또한, 본 발명의 입체 조형용 광경화성 수지 조성물은 가교제를 포함함으로써, 경화 밀도를 더욱 상승시켜 입체 조형용 광경화성 수지 조성물의 기계적 강도, 내열성 및 열변형 온도를 더욱 상승시킬 수 있다.In addition, the three-dimensional shaping photocurable resin composition of the present invention further increases the curing density by including a crosslinking agent, thereby further increasing the mechanical strength, heat resistance and heat distortion temperature of the three-dimensional shaping photocurable resin composition.
또한, 본 발명의 입체 조형용 광경화성 수지 조성물은 내열성 및 기계적 강도가 우수하여 광경화된 수지를 추후 공정 없이 바로 사용할 수 있는 장점을 지니고 있다.In addition, the photocurable resin composition for three-dimensional shaping of the present invention has excellent heat resistance and mechanical strength, so that the photocured resin can be used immediately without any subsequent process.
이하, 본 발명을 보다 자세히 설명한다.
Hereinafter, the present invention will be described in more detail.
본 발명은 양이온 경화성 단량체, 양이온성 광개시제, (메타)아크릴계 단량체, 광라디칼 발생제, 액정형 고분자 및 가교제를 포함하는 입체 조형용 광경화성 수지 조성물에 관한 것이다.
The present invention relates to a photocurable resin composition for three-dimensional shaping, comprising a cationic curable monomer, a cationic photoinitiator, a (meth)acrylic monomer, a photoradical generator, a liquid crystal polymer, and a crosslinking agent.
본 발명에서 슈퍼 엔지니어링 플라스틱(Super engineering plastic) 중 하나인 액정형 고분자를 입체 조형용 광경화성 수지 조성물의 성분으로 포함함으로써, 입체 조형용 광경화성 수지 조성물의 기계적 강도, 내열성 및 열변형 온도(Heat distortion temperature, HDT)를 향상시킬 수 있다.By including a liquid crystal polymer, which is one of the super engineering plastics in the present invention, as a component of the photocurable resin composition for three-dimensional molding, the mechanical strength, heat resistance, and heat distortion temperature of the photocurable resin composition for three-dimensional molding HDT) can be improved.
또한, 본 발명에서 가교제를 입체 조형용 광경화성 수지 조성물의 성분으로 포함함으로써, 경화밀도를 더욱 증가시켜 기계적 강도, 내열성 및 열변형 온도를 더욱 향상시킬 수 있다.
In addition, by including the crosslinking agent as a component of the photocurable resin composition for three-dimensional shaping in the present invention, it is possible to further increase the curing density to further improve mechanical strength, heat resistance, and heat distortion temperature.
(A)양이온 경화성 단량체(A) Cationic curable monomer
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 양이온 경화성 단량체는 에폭시 화합물, 옥세탄 화합물 및 비닐 에테르 화합물로 이루어진 군으로부터 선택되는 1종 이상을 포함한다.The cationic curable monomer contained in the photocurable resin composition for three-dimensional shaping of the present invention includes at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound.
상기 에폭시 화합물은 양이온성 광개시제의 존재 하에 양이온을 중합할 수 있는 작용기가 1개 또는 1개 이상을 포함하는 에폭시 화합물이면 그 종류를 특별히 한정하지 않는다. 상기 에폭시 화합물은 단량체성일 수 있고, 방향족 에폭시 화합물, 시클로지방족 에폭시 화합물, 헤테로시클릭 또는 지방족 에폭시 화합물일 수 있으며, 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The type of the epoxy compound is not particularly limited as long as it is an epoxy compound containing one or more than one functional group capable of polymerizing a cation in the presence of a cationic photoinitiator. The epoxy compound may be monomeric, an aromatic epoxy compound, a cycloaliphatic epoxy compound, a heterocyclic or aliphatic epoxy compound, and may be used alone or in combination of two or more.
상기 방향족 에폭시 화합물은 분자 내에 방향족기를 포함하는 에폭시 화합물을 의미하는 것으로, 예를 들면, 비스페놀 A계 에폭시, 비스페놀 F계 에폭시, 비스페놀 S계 에폭시 및 브롬화 비스페놀계 에폭시와 같은 비스페놀형 에폭시 수지; 페놀노볼락형 에폭시 수지 및 크레졸노볼락형 에폭시 수지와 같은 노볼락형 에폭시 수지; 크레졸 에폭시 및 레졸시놀글리시딜에테르 등이 사용될 수 있다. The aromatic epoxy compound refers to an epoxy compound containing an aromatic group in the molecule, and includes, for example, bisphenol-type epoxy resins such as bisphenol A-based epoxy, bisphenol F-based epoxy, bisphenol S-based epoxy, and brominated bisphenol-based epoxy; Novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; Cresol epoxy and resorcinol glycidyl ether and the like may be used.
상기 지환식 에폭시 화합물은 에폭시기가 지방족 고리를 구성하는 인접하는 2개의 탄소 원자 사이에 형성되어 있는 화합물을 의미하는 것으로, 예를 들면, 디시클로펜타디엔디옥사이드, 리모넨디옥사이드, 4-비닐시클로헥센디옥사이드, 2,4-에폭시시클로헥실메틸 3,4-에폭시시클로헥산카르복실레이트 및 비스(3,4-에폭시시클로헥실메틸)아디페이트 등이 사용될 수 있다. The alicyclic epoxy compound refers to a compound in which an epoxy group is formed between two adjacent carbon atoms constituting an aliphatic ring, for example, dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 2,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and bis(3,4-epoxycyclohexylmethyl) adipate and the like can be used.
상기 지방족 에폭시 화합물은 지방족 다가 알코올의 폴리글리시딜에테르; 지방족 다가 알코올의 알킬렌옥사이드 부가물의 폴리글리시딜에테르 등이 사용될 수 있다.The aliphatic epoxy compound is polyglycidyl ether of an aliphatic polyhydric alcohol; Polyglycidyl ether of an alkylene oxide adduct of an aliphatic polyhydric alcohol may be used.
상기 지방족 다가 알코올로는, 예를 들어 탄소수 2 내지 20의 지방족 다가 알코올일 수 있으며, 보다 구체적으로는, 에틸렌글리콜, 1,2-프로판디올, 1,3-프로판디올, 2-메틸-1,3-프로판디올, 2-부틸-2-에틸-1,3-프로판디올, 1,4-부탄디올, 네오펜틸글리콜, 3-메틸-2,4-펜탄디올, 2,4-펜탄디올, 1,5-펜탄디올, 3-메틸-1,5-펜탄디올, 2-메틸-2,4-펜탄디올, 2,4-디에틸-1,5-펜탄디올, 1,6-헥산디올, 1,7-헵탄디올, 3,5-헵탄디올, 1,8-옥탄디올, 2-메틸-1,8-옥탄디올, 1,9-노난디올 및 1,10-데칸디올 등의 지방족 디올; 시클로헥산디메탄올, 시클로헥산디올, 수소 첨가 비스페놀 A 및 수소 첨가 비스페놀 F 등의 지환식 디올; 트리메틸올에탄, 트리메틸올프로판, 헥시톨류, 펜티톨류, 글리세린, 폴리글리세린, 펜타에리트리톨, 디펜타에리트리톨, 폴리카프로락톤 및 테트라메틸올프로판 등의 3가 이상의 폴리올을 들 수 있다.The aliphatic polyhydric alcohol may be, for example, an aliphatic polyhydric alcohol having 2 to 20 carbon atoms, and more specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1, 5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1, Aliphatic diols such as 7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol and 1,10-decanediol; Alicyclic diols such as cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A and hydrogenated bisphenol F; Trimethylolethane, trimethylolpropane, hexitol, pentitol, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, polycaprolactone, and tetramethylolpropane.
또한, 상기 에폭시 화합물은 바람직하게는 3,4-에폭시시클로헥실메틸-3,4'-에폭시시클로헥산카복실레이트, 비스(3,4-에폭시 시클로 헥실메틸)아디페이트 디시클로펜타디엔 디옥사이드, 리모넨디옥사이드 및 4-비닐시클로헥센 디옥사이드로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.In addition, the epoxy compound is preferably 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, bis (3,4-epoxy cyclohexylmethyl) adipate dicyclopentadiene dioxide, limonene dioxide And it may be at least one selected from the group consisting of 4-vinylcyclohexene dioxide.
상기 양이온 경화성 단량체에 에폭시 화합물이 포함될 경우, 상기 에폭시 화합물은 단독으로 사용될 수 있으며, 옥세탄 화합물 및 비닐 에테르 화합물로 이루어진 군으로부터 선택되는 1종 이상과 혼용하여 사용될 수 있다.
When an epoxy compound is included in the cationic curable monomer, the epoxy compound may be used alone, and may be used in combination with at least one selected from the group consisting of an oxetane compound and a vinyl ether compound.
상기 옥세탄 화합물은 양이온성 광개시제가 존재할 때, 빛이 조사됨으로써 중합 또는 가교될 수 있다.The oxetane compound may be polymerized or crosslinked by irradiation with light when a cationic photoinitiator is present.
상기 옥세탄 화합물은 분자 내에 적어도 1개의 옥세타닐기를 갖는 것이면 특별히 한정되지 않으며, 당해 기술 분야에 잘 알려진 다양한 옥세탄 화합물을 사용할 수 있다. 또한, 상기 옥세탄 화합물은 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The oxetane compound is not particularly limited as long as it has at least one oxetanyl group in the molecule, and various oxetane compounds well known in the art may be used. In addition, the oxetane compound may be used alone or in combination of two or more.
본 발명의 상기 옥세탄 화합물로는, 예를 들면, 3-에틸-3-〔(3-에틸옥세탄-3-일)메톡시메틸〕옥세탄, 1,4-비스〔(3-에틸옥세탄-3-일)메톡시메틸〕벤젠, 1,4-비스〔(3-에틸옥세탄-3-일)메톡시〕벤젠, 1,3-비스〔(3-에틸옥세탄-3-일)메톡시〕벤젠, 1,2-비스〔(3-에틸옥세탄-3-일)메톡시〕벤젠, 4,4'-비스〔(3-에틸옥세탄-3-일)메톡시〕비페닐, 2,2'-비스〔(3-에틸옥세탄-3-일)메톡시〕비페닐, 3,3',5,5'-테트라메틸-4,4'-비스〔(3-에틸옥세탄-3-일)메톡시〕비페닐, 2,7-비스〔(3-에틸옥세탄-3-일)메톡시〕나프탈렌, 비스〔4-{(3-에틸옥세탄-3-일)메톡시}페닐〕메탄, 비스〔2-{(3-에틸옥세탄-3-일)메톡시}페닐〕메탄, 2,2-비스〔4-{(3-에틸옥세탄-3-일)메톡시}페닐〕프로판, 노볼락형페놀-포름알데히드 수지의 3-클로로메틸-3-에틸옥세탄에 의한 에테르화 변성물, 3(4),8(9)-비스〔(3-에틸옥세탄-3-일)메톡시메틸〕-트리시클로[5.2.1.0 2,6 ]데칸, 2,3-비스〔(3-에틸옥세탄-3-일)메톡시메틸〕노르보르난, 1,1,1-트리스〔(3-에틸옥세탄-3-일)메톡시메틸〕프로판, 1-부톡시-2,2-비스〔(3-에틸옥세탄-3-일)메톡시메틸〕부탄, 1,2-비스〔{2-(3-에틸옥세탄-3-일)메톡시}에틸티오〕에탄, 비스〔{4-(3-에틸옥세탄-3-일)메틸티오}페닐〕술피드, 비스〔{1-에틸(3-옥세타닐)}메틸〕에테르 및 1,6-비스〔(3-에틸옥세탄-3-일)메톡시〕-2,2,3,3,4,4,5,5-옥타플루오로헥산 등을 들 수 있다.As the oxetane compound of the present invention, for example, 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane, 1,4-bis[(3-ethyloxy) Cetan-3-yl)methoxymethyl]benzene, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetan-3-yl) ) Methoxy] benzene, 1,2-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 4,4'-bis [(3-ethyloxetan-3-yl) methoxy] ratio Phenyl, 2,2'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis[(3-ethyl Oxetan-3-yl)methoxy]biphenyl, 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene, bis[4-{(3-ethyloxetan-3-yl) )Methoxy}phenyl] methane, bis [2-{(3-ethyloxetan-3-yl) methoxy}phenyl] methane, 2,2-bis [4-{(3-ethyloxetan-3-yl) )Methoxy}phenyl]propane, a denatured product of novolac-type phenol-formaldehyde resin etherified with 3-chloromethyl-3-ethyloxetane, 3(4),8(9)-bis[(3-ethyl Oxetan-3-yl)methoxymethyl]-tricyclo[5.2.1.0 2,6]decane, 2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl] norbornane, 1 ,1,1-tris[(3-ethyloxetan-3-yl)methoxymethyl]propane, 1-butoxy-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl] Butane, 1,2-bis[{2-(3-ethyloxetan-3-yl)methoxy}ethylthio]ethane, bis[{4-(3-ethyloxetan-3-yl)methylthio}phenyl ]Sulfide, bis[{1-ethyl(3-oxetanyl)}methyl] ether and 1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3 ,4,4,5,5-octafluorohexane, etc. are mentioned.
상기 양이온 경화성 단량체에 옥세탄 화합물이 포함될 경우, 상기 옥세탄 화합물은 단독으로 사용될 수 있으며, 에폭시 화합물 및 비닐 에테르 화합물로 이루어진 군으로부터 선택되는 1종 이상과 혼용하여 사용될 수 있다.
When an oxetane compound is included in the cationic curable monomer, the oxetane compound may be used alone, and may be used in combination with one or more selected from the group consisting of an epoxy compound and a vinyl ether compound.
또한, 상기 에폭시 화합물, 옥세탄 화합물 및 비닐 에테르 화합물로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 양이온 경화성 단량체는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량이 100 중량%가 되도록 잔량을 포함한다.
In addition, the cationically curable monomer comprising at least one selected from the group consisting of the epoxy compound, the oxetane compound, and the vinyl ether compound contains the remaining amount so that the total weight of the photocurable resin composition for stereoscopic molding of the present invention is 100% by weight. .
(B)(B) 양이온성Cationic 광개시제Photoinitiator
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 양이온성 광개시제는 활성 에너지 선의 조사에 의해 양이온(cation) 종이나 루이스산을 만들어내는 화합물로서, 상기 사용되는 활성 에너지 선은 가시광선, 자외선, 적외선, X선, α선, β선 및 γ선 등을 의미한다. The cationic photoinitiator contained in the photocurable resin composition for three-dimensional shaping of the present invention is a compound that generates cation species or Lewis acid by irradiation with active energy rays, and the active energy rays used are visible rays, ultraviolet rays, infrared rays, It means X-rays, α-rays, β-rays, and γ-rays.
상기 양이온성 광개시제는 광 노출 시에 루이스 산을 방출하는 하기 화학식 5의 오늄(onium) 염을 사용하는 것이 바람직하나, 이에 한정되는 것은 아니다. The cationic photoinitiator is preferably an onium salt of Formula 5 that releases Lewis acid upon exposure to light, but is not limited thereto.
[화학식 4][Formula 4]
[R1 aR2 bR3 cR4 dW]+p[MXq +p]-p [R 1 a R 2 b R 3 c R 4 d W] +p [MX q +p ] -p
상기 [R1 aR2 bR3 cR4 dW]+p는 오늄 이온이고,The [R 1 a R 2 b R 3 c R 4 d W] +p is an onium ion,
상기 W는 S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl 또는 -N=N기 이고,W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or -N=N group,
상기 R1, R2, R3 및 R4는 각각 동일하거나 상이한 유기 작용기이고, The R 1 , R 2 , R 3 and R 4 are each the same or different organic functional groups,
상기 a, b, c 및 d는 각각 0 내지 3의 정수이고, Wherein a, b, c and d are each an integer of 0 to 3,
상기 a+b+c+d=p 이고, Wherein a+b+c+d=p,
상기 [MXq +p]는 할로겐 착화합물이고,The [MX q +p ] is a halogen complex compound,
상기 M은 B, P, As, Sb, Fe, Sn,Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn 또는 Co 이고, The M is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn or Co,
상기 X는 F, Cl 또는 Br 등의 할로겐 원자이고, X is a halogen atom such as F, Cl or Br,
상기 p는 할로겐 착화합물 이온의 순 전하(net charge)이고, P is the net charge of the halogen complex ions,
상기 q는 M의 원자가이다.
Q is the valence of M.
상기 화학식 4에서 [MXq +p]-p의 구체적인 예로는, 테트라플루오로보레이트(BF4 -), 헥사플루오로포스페이트(PF6 -), 헥사플루오로안티모네이트(SbF6 -), 헥사플루오로아세네이트(AsF6 -) 및 헥사클로로안티모네이트(SbCl6 -) 등을 들 수 있다.In the above formula (4) Specific examples of [MX p + q] -p is, tetrafluoroborate (BF 4 -), phosphate (PF 6 -) hexafluoropropane, antimonate hexafluorophosphate (SbF 6 -), hexamethylene and the like can be mentioned acetoxy carbonate (AsF 6 - -) fluoro, and hexachloro antimonate (SbCl 6).
또한, [MXq +p]-p 이외에 [MXq(OH)-]로 표시되는 음이온을 갖는 오늄염이 사용될 수 있으며, 퍼클로르산 이온(ClO4 -), 트리플루오로메탄설폰산 이온(CF3SO3 -), 플루오로설폰산 이온(FSO3 -), 톨루엔설폰산 이온, 트리니트로벤젠설폰산 음이온 및 트니니트로톨루엔설폰산 음이온이 또한 사용될 수 있다.In addition, [MX p + q] -p addition [MX q (OH) -] o and salts may be used having an anion represented by the buffer chlor acid ion (ClO 4 -), methanesulfonic acid ion trifluoroacetate ( CF3SO 3 -), sulfonate ion (FSO 3-fluoro-a), toluenesulfonic acid ion, benzenesulfonic acid anion, and trinitrotoluene teuni nitrotoluene sulfonic acid anion can also be used.
상기 음이온을 갖는 오늄 염 중, 방향족 오늄 염이 성분으로서 특히 효과적이다. 이들 중, JP-A-50-151996 호 및 JP-A-50-158680 호에 개시된 방향족 할로늄 염; JP-A-50-151997 호, JP-A-52-30899 호, JP-A-56-55420 호 및 JP-A-55-125105 호에 개시된 VIA기 방향족 오늄 염; JP-A-50-158698 호에 개시된 VA 기 방향족 오늄 염; JP-A-56-8428호, JP-A-56-149402 호 및 JP-A-57-192429 호에 개시된 옥소설폭스오늄 염; JP-A-49-17040 호에 개시된 방향족다이아조늄 염; USP 4,139,655 호에 개시된 티오피릴륨 염; 등이 바람직하다. Of the onium salts having an anion, an aromatic onium salt is particularly effective as a component. Among these, aromatic halonium salts disclosed in JP-A-50-151996 and JP-A-50-158680; VIA group aromatic onium salts disclosed in JP-A-50-151997, JP-A-52-30899, JP-A-56-55420 and JP-A-55-125105; VA group aromatic onium salt disclosed in JP-A-50-158698; Oxosulfoxide onium salts disclosed in JP-A-56-8428, JP-A-56-149402 and JP-A-57-192429; Aromatic diazonium salts disclosed in JP-A-49-17040; The thiopyryllium salt disclosed in USP 4,139,655; And the like are preferred.
또한, 양이온성 광개시제로 철/알렌 착체 개시제, 알루미늄 착체/광분해 규소 화합물 개시제 등이 사용될 수 있다.In addition, as the cationic photoinitiator, an iron/allene complex initiator, an aluminum complex/photodegradable silicon compound initiator, and the like may be used.
상기 양이온성 광개시제의 시판품의 예로는, UVI-6950, UVI-6970, UVI-6974 및 UVI-6990(유니온 카바이드 코포레이션 제조), 아데카오프토머 SP-150, SP-151, SP-170 및 SP-172(아사히 덴카 코교캄파니 리미티드 제조), 이가큐어(Irgacure) 261(시바 스페셜티 케미칼즈 캄파니 리미티드 제조), CI-2481, CI-2624, CI-2639 및 CI-2064(닛폰 소다 캄파니 리미티드(Nippon Soda Co., Ltd.) 제조), CD-1010, CD-1011 및 CD-1012(사토머(Sartomer) 캄파니 제조), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103(미도리 케미칼 캄파니 리미티드 제조), PCI-061T, PCI-062T, PCI-020T 및 PCI-022T(재팬 카야쿠 캄파니 리미티드 제조) 등을 들 수 있다. 이들 중, UVI-6970, UVI-6974, 아데카오프토머 SP-170, SP-172, CD-1012 및 MPI-103은 높은 광경화 감도를 발현시킬 수 있으므로 특히 바람직하다.Examples of commercially available products of the cationic photoinitiator include UVI-6950, UVI-6970, UVI-6974 and UVI-6990 (manufactured by Union Carbide Corporation), adecaoptomers SP-150, SP-151, SP-170 and SP- 172 (manufactured by Asahi Denka Kogyo Company Limited), Irgacure 261 (manufactured by Shiba Specialty Chemicals Company Limited), CI-2481, CI-2624, CI-2639 and CI-2064 (Nippon Soda Company Limited ( Nippon Soda Co., Ltd.), CD-1010, CD-1011 and CD-1012 (manufactured by Sartomer Company), DTS-102, DTS-103, NAT-103, NDS-103, TPS -103, MDS-103, MPI-103, BBI-103 (manufactured by Midori Chemical Company Limited), PCI-061T, PCI-062T, PCI-020T, and PCI-022T (manufactured by Japan Kayaku Company Limited), etc. I can. Among these, UVI-6970, UVI-6974, adecaoptomers SP-170, SP-172, CD-1012 and MPI-103 are particularly preferable because they can express high photocuring sensitivity.
상기 양이온성 광개시제는 단독 또는 2종 이상 조합하여 사용할 수 있다.The cationic photoinitiators may be used alone or in combination of two or more.
상기 양이온성 광개시제는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량에 대하여, 0.1 내지 5 중량%로 포함되며, 바람직하게는 0.5 내지 3 중량% 로 포함된다. The cationic photoinitiator is included in an amount of 0.1 to 5% by weight, and preferably 0.5 to 3% by weight, based on the total weight of the three-dimensional shaping photocurable resin composition of the present invention.
상기 양이온성 광개시제가 0.1 중량% 미만으로 포함되면 감도의 저하로 제조 공정시간이 길어지고, 제조된 입체 조형물의 강도가 저하되는 문제가 있고, 5 중량%를 초과하여 포함되면 감도는 증가되나, 가격적으로 고가인 개시제의 과량 사용에 의한 비용 문제가 발생한다. 또한, 양이온성 광개시제는 경화성 물질이 아니므로, 오히려 입체 조형물의 기계적 강도의 저하를 유발할 수 있다.
If the cationic photoinitiator is included in an amount of less than 0.1% by weight, the manufacturing process time is prolonged due to a decrease in sensitivity, and there is a problem that the strength of the manufactured three-dimensional sculpture decreases. If it is included in excess of 5% by weight, the sensitivity is increased, but the price In general, there is a cost problem due to excessive use of an expensive initiator. In addition, since the cationic photoinitiator is not a curable material, it may cause a decrease in mechanical strength of the three-dimensional sculpture.
(C)((C)( 메타Meta )아크릴계 단량체)Acrylic monomer
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 (메타)아크릴계 단량체는 라디칼 중합성 모노머로 라디칼 반응성 작용기를 갖는 화합물들이면 그 종류를 특별히 한정하지 않으나, 바람직하게는 관능기인 (메타)아크릴로일기를 분자 내에 1개 이상 갖고 있는 (메타)아크릴레이트류, (메타)아크릴아미드류, 말레이미드류, (메타)아크릴산, 말레인산, 이타콘산, (메타)아크릴알데히드, (메타)아크릴로일모르폴린, N-비닐-2-피롤리돈 및 트리알릴이소시아누레이트 등을 사용할 수 있다.The (meth)acrylic monomer included in the stereolithographic photocurable resin composition of the present invention is a radical polymerizable monomer and is not particularly limited as long as it is a compound having a radical reactive functional group, but preferably a functional group (meth)acryloyl group (Meth)acrylates, (meth)acrylamides, maleimides, (meth)acrylic acid, maleic acid, itaconic acid, (meth)acrylaldehyde, (meth)acryloylmorpholine, which have one or more in the molecule, N-vinyl-2-pyrrolidone, triallyl isocyanurate, and the like can be used.
상기 분자 내에 1개의 (메타)아크릴로일기를 갖는 단관능 아크릴 단량체로서 (메타)아크릴레이트류를 구체적으로 예를 들면, 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 부틸(메타)아크릴레이트, 이소부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트, 1,4-시클로헥산디메틸롤모노(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 디시클로펜테닐(메타)아크릴레이트, 디시클로펜테닐옥시에틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 페놀알킬렌옥사이드 부가물의 (메타)아크릴레이트, p-쿠밀페놀알킬렌옥사이드 부가물의 (메타)아크릴레이트, o-페닐페놀알킬렌옥사이드 부가물의 (메타)아크릴레이트, 노닐페놀알킬렌옥사이드 부가물의 (메타)아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 에톡시에톡시에틸(메타)아크릴레이트, 2-에틸헥실알콜의 알킬렌옥사이드 부가물의 (메타)아크릴레이트, 에틸렌글리콜모노(메타)아크릴레이트, 프로필렌글리콜모노(메타)아크릴레이트, 펜탄디올모노(메타)아크릴레이트, 헥산디올모노(메타)아크릴레이트, 디에틸렌글리콜의 모노(메타)아크릴레이트, 트리에틸렌글리콜의 모노(메타)아크릴레이트, 테트라에틸렌글리콜의 모노(메타)아크릴레이트, 폴리에틸렌글리콜의 모노(메타)아크릴레이트, 디프로필렌글리콜의 모노(메타)아크릴레이트, 트리프로필렌글리콜의 모노(메타)아크릴레이트, 폴리프로필렌글리콜의 모노(메타)아크릴레이트, 2-히드록시-3-페녹시프로필(메타)아크릴레이트, 2-히드록시-3-부톡시프로필(메타)아크릴레이트, 테트라히드로푸르푸릴(메타)아크릴레이트, 카프로락톤 변성 테트라히드로 푸르푸릴(메타)아크릴레이트, (2-에틸-2-메틸-1,3-디옥솔란-4-일)메틸(메타)아크릴레이트, (2-이소부틸-2-메틸-1,3-디옥솔란-4-일)메틸(메타)아크릴레이트, (1,4-디옥사스피로[4,5]데칸-2-일)메틸(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 3,4-에폭시시클로헥실메틸(메타)아크릴레이트, (3-에틸옥세탄-3-일)메틸(메타)아크릴레이트, 2-(메타)아크릴로일옥시메틸이소시아네이트, 알릴(메타)아크릴레이트, N-(메타)아크릴로일옥시에틸헥사히드로프탈이미드, N-(메타)아크릴로일옥시에틸테트라히드로프탈이미드, 2-(메타)아크릴로일옥시에틸헥사히드로프탈산, 2-(메타)아크릴로일옥시에틸숙신산, ω-카르복시-폴리카프로락톤모노(메타)아크릴레이트 및 2-(메타)아크릴로일옥시에틸애시드포스페이트 등을 들 수 있다.Specific examples of (meth)acrylates as monofunctional acrylic monomers having one (meth)acryloyl group in the molecule include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylic Rate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, Lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclo Hexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate of adduct of phenolalkylene oxide, (meth)acrylate of adduct of p-cumylphenolalkylene oxide, o-phenylphenol (Meth)acrylate of an alkylene oxide adduct, (meth)acrylate of a nonylphenol alkylene oxide adduct, 2-methoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-ethylhexyl (Meth)acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, di Ethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) Acrylate, mono(meth)acrylate of tripropylene glycol, mono(meth)acrylate of polypropylene glycol, 2-hydroxy-3-phenoxypropyl(meth)acrylate, 2-hydroxy-3-butoxy Propyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (2-ethyl-2-methyl-1,3-dioxolane -4-yl)methyl(meth)acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, (1,4-dioxaspiro[4) ,5]decan-2-yl)methyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl) Methyl(meth)acrylate, 2-(meth)acryloyloxymethylisocyanate, allyl(meth)acrylate, N-(meth)acryloyloxyethylhexahydrophthalimide, N-(meth)acryloyl Oxyethyltetrahydrophthalimide, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, ω-carboxy-polycaprolactone mono(meth)acrylate and 2- (Meth)acryloyloxyethyl acid phosphate, etc. are mentioned.
상기 분자 내에 1개의 (메타)아크릴로일기를 갖는 단관능 아크릴 단량체로서 (메타)아크릴아미드류를 구체적으로 예를 들면, (메타)아크릴아미드, N,N-디메틸(메타)아크릴아미드, N,N-디에틸(메타)아크릴아미드, N-메틸롤(메타)아크릴아미드, N-(3-N,N-디메틸아미노프로필)(메타)아크릴아미드, 메틸렌비스(메타)아크릴아미드, 에틸렌비스(메타)아크릴아미드 및 N,N-디알릴(메타)아크릴아미드 등을 들 수 있다.Specific examples of (meth)acrylamides as monofunctional acrylic monomers having one (meth)acryloyl group in the molecule include (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N, N-diethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-(3-N,N-dimethylaminopropyl)(meth)acrylamide, methylenebis(meth)acrylamide, ethylenebis( Meth)acrylamide and N,N-diallyl (meth)acrylamide, and the like.
상기 말레이미드류를 구체적으로 예를 들면, N-메틸말레이미드, N-히드록시에틸말레이미드, N-히드록시에틸시트라콘이미드, N-히드록시에틸시트라콘이미드 및 이소포론디이소시아네이트의 우레탄아크릴레이트 등을 들 수 있다.Specific examples of the maleimides are N-methylmaleimide, N-hydroxyethylmaleimide, N-hydroxyethylcitraconimide, N-hydroxyethylcitraconimide, and isophorone diisocyanate. Urethane acrylate, etc. are mentioned.
상기 분자 내에 2개의 (메타)아크릴로일기를 갖는 2관능 아크릴 단량체로서 (메타)아크릴레이트류를 구체적으로 예를 들면, 1,3-부탄다이올디(메타)아크릴레이트, 1,6-헥산다이올디(메타)아크릴레이트, 1,9-노난다이올디(메타)아크릴레이트, 1,10-데칸다이올디(메타)아크릴레이트, 1,3-부틸렌글리콜디(메타)아크릴레이트, 2-메타아크릴로일옥시에틸에시트포스페이트, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 사이클로헥산디메탄올디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜(200)디(메타)아크릴레이트, 폴리에틸렌글리콜(400)디(메타)아크릴레이트, 폴리에틸렌글리콜(600)디(메타)아크릴레이트, 글리세린디(메타)아크릴레이트, 2-히드록시-3-아크릴로옥시프로필메타아크릴레이트 및 디메틸롤트리사이크로데칸디(메타)아크릴레이트 등을 들 수 있다.Specific examples of (meth)acrylates as a bifunctional acrylic monomer having two (meth)acryloyl groups in the molecule, for example, 1,3-butanedioldi(meth)acrylate, 1,6-hexanedi Oldy(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 2-meth Acryloyloxyethyl Esit Phosphate, Ethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Dipropylene Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol (200) di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, polyethylene glycol (600) di (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acrylic Rooxypropyl methacrylate and dimethylol tricyclodecanedi (meth)acrylate, etc. are mentioned.
상기 분자 내에 3개의 (메타)아크릴로일기를 갖는 다관능 아크릴 단량체로서 (메타)아크릴레이트류를 구체적으로 예를 들면, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판 트리(메타)아크릴레이트, 디트리메틸올프로판트리(메타)아크릴레이트, 트리메틸프로판트리(메타)아크릴레이트, 트리(2-히드록시에틸)이소시안우레이트트리아크릴레이트, 트리(2-히드록시에틸)이소시아우레이트, 펜타리트리톨트리아크릴레이트, 에톡시레이트 트리메틸올프로판트리(메타)아크릴레이트 및 프록시레이트트리메틸올프로판트리(메타)아크릴레이트 등을 들 수 있다.Specific examples of (meth)acrylates as polyfunctional acrylic monomers having three (meth)acryloyl groups in the molecule, for example, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate , Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, trimethylpropane tri(meth)acrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, tri(2) -Hydroxyethyl)isosiaurate, pentarititol triacrylate, ethoxylate trimethylolpropane tri(meth)acrylate, proxirate trimethylolpropane tri(meth)acrylate, etc. are mentioned.
상기 분자 내에 4개 또는 5개의 (메타)아크릴로일기를 갖는 다관능 아크릴 단량체로서 (메타)아크릴레이트류를 구체적으로 예를 들면, 펜타리트리톨테트라(메타)아크릴레이트, 디트리메틸올프로란테트라(메타)아크릴레이트, 디펜타리트리톨펜타(메타)아크릴레이트, 에폭시레이트펜타리트리톨테트라(메타)아크릴레이트 및 펜타아크릴레이트에스터 등을 들 수 있다.Specific examples of (meth)acrylates as polyfunctional acrylic monomers having 4 or 5 (meth)acryloyl groups in the molecule are, for example, pentarititol tetra(meth)acrylate, ditrimethylolprorantetra (Meth)acrylate, dipentarithritol penta (meth)acrylate, epoxide pentarititol tetra (meth)acrylate, pentaacrylate ester, etc. are mentioned.
상기 분자 내에 6개의 (메타)아크릴로일기를 갖는 다관능 아크릴 단량체로서 (메타)아크릴레이트류를 구체적으로 예를 들면, 디펜타리트리톨헥사(메타)아크릴레이트를 들 수 있다.Specific examples of (meth)acrylates as a polyfunctional acrylic monomer having six (meth)acryloyl groups in the molecule include dipentarithritol hexa(meth)acrylate.
상기 (메타)아크릴계 단량체는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량에 대하여 1 내지 40 중량% 이하로 포함되며, 바람직하게는 5 내지 30 중량%, 더욱 바람직하게는 5 내지 25 중량%로 포함된다. The (meth)acrylic monomer is contained in an amount of 1 to 40% by weight or less, preferably 5 to 30% by weight, more preferably 5 to 25% by weight, based on the total weight of the three-dimensional shaping photocurable resin composition of the present invention. do.
상기 (메타)아크릴계 단량체가 1 중량% 미만으로 포함되면 본 발명의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물의 기계적 강도가 향상되지 않으며, 40 중량%를 초과할 경우 광경화시 수축이 심해지는 문제점이 발생한다.
If the (meth)acrylic monomer is included in an amount of less than 1% by weight, the mechanical strength of the three-dimensional sculpture made of the photocurable resin composition for three-dimensional molding of the present invention is not improved, and if it exceeds 40% by weight, the shrinkage is severe during photocuring. A problem arises.
(D)(D) 광라디칼Optical radical 발생제Generator
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 광라디칼 발생제는 그 종류를 특별히 한정하는 것은 아니나, 바람직하게는 트리아진계 화합물, 아세토페논계 화합물, 비이미다졸계 화합물, 벤조페논계 화합물 및 티오크산톤계 화합물 및 벤조인에테르계 화합물로 이루어진 군으로부터 선택되는 1종 이상을 사용할 수 있다.The photo-radical generator contained in the photocurable resin composition for three-dimensional shaping of the present invention does not specifically limit the kind, but preferably, a triazine-based compound, an acetophenone-based compound, a biimidazole-based compound, a benzophenone-based compound, and Ti One or more selected from the group consisting of an oxanthone compound and a benzoin ether compound may be used.
상기 트리아진계 화합물은 예를 들어, 2,4-비스(트리클로로메틸)-6-(4-메톡시페닐)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-(4-메톡시나프틸)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-피페로닐-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-(4-메톡시스티릴)-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(5-메틸푸란-2-일)에테닐]-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(푸란-2-일)에테닐]-1,3,5-트리아진, 2,4-비스(트리클로로메틸)-6-[2-(4-디에틸아미노-2-메틸페닐)에테닐]-1,3,5-트리아진 및 2,4-비스(트리클로로메틸)-6-[2-(3,4-디메톡시페닐)에테닐]-1,3,5-트리아진 등을 들 수 있다.The triazine-based compound is, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2 -Yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloro Methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.
상기 아세토페논계 화합물은 예를 들어, 디에톡시아세토페논, 2-하이드록시-2-메틸-1-페닐프로판-1-온, 벤질디메틸케탈, 2-하이드록시-1-[4-(2-하이드록시에톡시)페닐]-2-메틸프로판-1-온, 1-하이드록시사이클로헥실페닐케톤, 2-메틸-1-(4-메틸티오페닐)-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부탄-1-온 및 2-하이드록시-2-메틸-1-[4-(1-메틸비닐)페닐]프로판-1-온의 올리고머 등을 들 수 있다.The acetophenone-based compound is, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane- 1-one oligomers, etc. are mentioned.
상기 비이미다졸계 화합물은 예를 들어, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(알콕시페닐)비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(디알콕시페닐)비이미다졸, 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라(트리알콕시페닐)비이미다졸 및 4,4',5,5'-위치의 페닐기가 카보알콕시기에 의해 치환되어 있는 이미다졸 화합물 등을 들 수 있고, 바람직하게는 2,2'-비스(2-클로로페닐)-4,4',5,5'-테트라페닐비이미다졸 및 2,2'-비스(2,3-디클로로페닐)-4,4',5,5'-테트라페닐비이미다졸을 들 수 있다.The biimidazole-based compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3 -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole and 4, And imidazole compounds in which the phenyl group at the 4',5,5'-position is substituted by a carboalkoxy group, and the like, preferably 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetraphenylbiimidazole and 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.
상기 벤조페논계 화합물은 예를 들어, 벤조페논, 0-벤조일벤조산 메틸, 4-페닐벤조페논, 4-벤조일-4'-메틸디페닐술피드, 3,3',4,4'-테트라(tert-부틸퍼옥시카르보닐)벤조페논 및 2,4,6-트리메틸벤조페논 등을 들 수 있다.The benzophenone-based compound is, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, and the like.
상기 티오크산톤계 화합물은 예를 들어, 2-이소프로필티오크산톤, 2,4-디에틸티오크산톤, 2,4-디클로로티오크산톤 및 1-클로로-4-프로폭시티오크산톤 등을 들 수 있다.The thioxanthone compound is, for example, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. Can be mentioned.
상기 벤조인에테르계 화합물은 예를 들어, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르 및 벤조인이소뷰틸에테르 등을 들 수 있다.Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
상기 광라디칼 발생제는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량에 대하여 0.5 내지 10 중량%로 포함되며, 바람직하게는 0.5 내지 8 중량% 로 포함된다. The photo-radical generator is included in an amount of 0.5 to 10% by weight, and preferably 0.5 to 8% by weight, based on the total weight of the three-dimensional shaping photocurable resin composition of the present invention.
상기 광라디칼 발생제가 0.5 중량% 미만으로 포함되면 감도의 저하로 제조 공정시간이 길어지고, 제조된 입체 조형물의 강도가 저하되는 문제가 있고, 10 중량%를 초과하여 포함되면 감도는 증가되나, 내크랙성의 우려가 발생될 수 있다.
If the photo-radical generator is contained in an amount of less than 0.5% by weight, the manufacturing process time is prolonged due to a decrease in sensitivity, and the strength of the manufactured three-dimensional sculpture decreases. If it is included in excess of 10% by weight, the sensitivity is increased. There may be concerns about cracking.
상기 양이온 경화성 단량체(A)는 양이온성 광개시제(B)에 의하여 경화가 일어나며, 상기 (메타)아크릴계 단량체(C)는 광라디칼 발생제(D)에 의하여 경화가 일어난다.The cationic curable monomer (A) is cured by a cationic photoinitiator (B), and the (meth)acrylic monomer (C) is cured by a photo radical generator (D).
그러나 입체 조형용 광경화성 수지의 경화 후, 추가적인 경화가 필요한 공정에서는 양이온 경화성 단량체가 양이온성 광개시제에 의해서만 경화가 일어난다고 볼 수는 없으며, (메타)아크릴계 단량체가 광라디칼 발생제에 의해서만 경화가 일어난다고는 볼 수 없다.
However, in the process requiring additional curing after curing of the photocurable resin for stereoscopic molding, it cannot be considered that curing occurs only by the cationic photoinitiator, and that the (meth)acrylic monomer is cured only by the photoradical generator. Can't see
(E)액정형 고분자(E) Liquid crystal polymer
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 액정형 고분자(Liquid crystal polymer, LCP)는 슈퍼 엔지니어링 플라스틱(Super engineering plastic)의 종류 중 하나로, 수십 μm 이하의 크기를 가진 입자이며, 높은 탄성율, 강도 및 내열성을 가져 경화 후에 열 또는 경시에 의한 변형이 적고, 기계적 강도가 우수한 것이 특징이다. Liquid crystal polymer (LCP) included in the photocurable resin composition for three-dimensional shaping of the present invention is one of the types of super engineering plastics, and is a particle having a size of tens of μm or less, and has a high modulus of elasticity and strength. And heat resistance, less deformation due to heat or aging after curing, and excellent mechanical strength.
따라서, 상기 액정형 고분자의 상기 특징을 이용하여 본 발명의 입체 조형용 광경화성 수지 조성물 성분 중 하나로 액정형 고분자를 포함하면, 필러로써의 역할을 수행하여 우수한 강성 및 인성을 나타내는 입체 조형물을 제조할 수 있다. Therefore, when the liquid crystal polymer is included as one of the components of the photocurable resin composition for three-dimensional molding of the present invention by using the above characteristics of the liquid crystal polymer, it is possible to prepare a three-dimensional sculpture showing excellent rigidity and toughness by performing the role as a filler. have.
또한, 상기 액정형 고분자의 비중은 액정 고분자 이외에 본 발명의 입체 조형용 광경화성 수지 조성물인 양이온 경화성 단량체, 양이온성 광개시제, (메타)아크릴계 단량체, 광라디칼 발생제 및 가교제와 비중이 비슷하여 조성물 제조시 분산 공정이 용이한 장점을 지니고 있다.In addition, the specific gravity of the liquid crystal polymer is similar to that of the cationically curable monomer, cationic photoinitiator, (meth)acrylic monomer, photoradical generator, and crosslinking agent, which are the photocurable resin composition for three-dimensional molding of the present invention in addition to the liquid crystal polymer. It has the advantage of easy dispersion process.
상기 액정형 고분자는 열변형온도가 250℃ 이상이면 그 종류에 관계없이 사용할 수 있다. 본 발명에서 사용할 수 있는 액정형 고분자로는 바람직하게는 스미카슈퍼(Sumikasuper) E4000, E5000, E6000 시리즈(Sumitomo), 사이다(Xydar) MG850, G930(Solvay advenced polymer), 제나이트(Zenite) 5145L(Dupont), 벡트라(Vectra) 100시리즈, 200시리즈(Ticona) 및 시베라스(Siveras) L304시리즈(Toray) 등이 있다.The liquid crystal polymer can be used regardless of its type as long as the heat deflection temperature is 250°C or higher. Liquid crystal polymers usable in the present invention are preferably Sumikasuper E4000, E5000, E6000 series (Sumitomo), Xydar MG850, G930 (Solvay advenced polymer), Zenite 5145L (Dupont ), Vectra 100 series, 200 series (Ticona) and Siveras L304 series (Toray).
상기 액정형 고분자는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량에 대하여 2 내지 30 중량% 이하로 포함되며, 바람직하게는 5 내지 20 중량%, 더욱 바람직하게는 8 내지 13 중량%로 포함된다. The liquid crystal polymer is included in an amount of 2 to 30% by weight or less, preferably 5 to 20% by weight, and more preferably 8 to 13% by weight, based on the total weight of the three-dimensional shaping photocurable resin composition of the present invention.
상기 액정형 고분자가 2 중량% 미만으로 포함되면 필러로써의 기계적 강도의 향상 효과가 부족하고, 30 중량%를 초과하여 포함되면 입체 조형용 광경화성 수지 조성물의 점도가 상승하여 입체 조형물의 제조 속도가 저하되고, 제조된 조형물의 정밀도가 저하되는 문제점이 발생한다.
When the liquid crystal polymer is contained in an amount of less than 2% by weight, the effect of improving the mechanical strength as a filler is insufficient, and when it is included in an amount exceeding 30% by weight, the viscosity of the photocurable resin composition for three-dimensional molding increases and the manufacturing speed of the three-dimensional sculpture decreases. And, there is a problem that the precision of the manufactured sculpture is lowered.
(F)(F) 가교제Crosslinking agent
본 발명의 입체 조형용 광경화성 수지 조성물에 포함되는 가교제(Cross-linker)는 광경화시, 양이온성 광개시제에 의해 발생한 산에 의한 수산기, 에폭시기 및 아크릴기가 액정형 고분자 입자들과 경화되어, 가교 중합체 매트릭스(cross-linked polymer matrix)를 형성하여 입체 조형용 광경화성 수지 조성물의 기계적 강도 및 내열성을 향상시킬 수 있다.The cross-linker included in the photocurable resin composition for three-dimensional shaping of the present invention is a cross-linker that, during photocuring, a hydroxyl group, an epoxy group, and an acrylic group by an acid generated by a cationic photoinitiator are cured with liquid crystal polymer particles, and a crosslinked polymer matrix By forming a (cross-linked polymer matrix), it is possible to improve mechanical strength and heat resistance of the photocurable resin composition for three-dimensional shaping.
상기 가교제는 그 종류를 특별히 한정하지는 않으나, 바람직하게는 하기 화학식 1 내지 3으로 이루어진 군으로부터 선택되는 1종 이상을 포함한다.The type of the crosslinking agent is not particularly limited, but preferably includes at least one selected from the group consisting of the following Chemical Formulas 1 to 3.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 R은 수소 또는 메틸기이다.R is hydrogen or a methyl group.
또한, 상기 가교제는 본 발명의 입체 조형용 광경화성 수지 조성물 총 중량에 대하여 3 내지 15 중량%로 포함되며, 바람직하게는 5 내지 10 중량%로 포함된다.In addition, the crosslinking agent is included in an amount of 3 to 15% by weight, preferably 5 to 10% by weight, based on the total weight of the three-dimensional shaping photocurable resin composition of the present invention.
상기 가교제의 함량이 3 중량% 미만으로 포함되면, 충분한 가교가 이루어지지 않아 기계적 강도가 향상되지 않고, 15 중량%를 초과하여 포함되면, 잔존하는 가교제의 양이 많아져 오히려 기계적 강도가 낮아지는 경향이다.
When the content of the crosslinking agent is less than 3% by weight, sufficient crosslinking is not achieved and the mechanical strength is not improved, and when it is included in excess of 15% by weight, the amount of the remaining crosslinking agent increases and the mechanical strength tends to decrease. to be.
본 발명의 입체 조형용 광경화성 수지 조성물은 액정형 고분자 및 가교제를 포함함으로써, 본 발명의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물의 열변형온도가 70℃ 이상을 나타내며, 아이조도 충격강도는 40J/cm 이상을 나타낼 수 있다. The three-dimensional molding photocurable resin composition of the present invention contains a liquid crystal polymer and a crosslinking agent, so that the three-dimensional molding made of the three-dimensional molding photocurable resin composition of the present invention exhibits a heat deformation temperature of 70°C or higher, and the Izodo impact strength is 40J. May represent more than /cm.
따라서, 본 발명의 입체 조형용 광경화성 수지 조성물은 기계적 강도 및 내열성이 향상된 입체 조형물을 제조할 수 있어, 후 처리 없이 곧바로 전자 장치 등의 부품 등으로 사용이 가능하다.
Accordingly, the photocurable resin composition for three-dimensional molding of the present invention can produce a three-dimensional sculpture with improved mechanical strength and heat resistance, and can be used directly as a component such as an electronic device without post-treatment.
본 발명의 입체 조형용 광경화성 수지 조성물은 양이온 경화성 단량체의 경화 속도를 향상시키기 위하여 추가로 폴리올을 포함할 수 있으며, 바람직하게는 폴리에테르 폴리올 화합물을 포함할 수 있다. 상기 폴리에테르 폴리올 화합물은 입체 조형용 광경화성 수지 조성물의 광경화성을 증가시켜, 광 경화에 의해 수득되는 3차원 입체 조형물의 시간 경과에 따른 억압 변형이 일어나지 않도록 형태를 안정하게 유지할 수 있도록 하며, 기계적 특성의 억압 변화를 개선할 수 있는 물리적 안정성을 향상시키는 역할을 한다. The photocurable resin composition for three-dimensional shaping of the present invention may additionally contain a polyol in order to improve the curing speed of the cationic curable monomer, and preferably a polyether polyol compound. The polyether polyol compound increases the photocurability of the photocurable resin composition for three-dimensional molding, thereby stably maintaining the shape of the three-dimensional three-dimensional sculpture obtained by photo-curing so that suppressive deformation over time does not occur, and mechanical properties It plays a role in improving physical stability, which can improve the oppressive change of
상기 폴리에테르 폴리올 화합물은 1 분자 내에 3개 이상, 바람직하게는 1 분자 내에 3 내지 6개의 하이드록실기를 갖는 것을 사용한다. 1 분자 내에 3개 미만의 하이드록실기를 갖는 폴리에테르 폴리올 화합물은 입체 조형용 광경화성 수지 조성물의 광경화성을 불충분하게 하고, 제조된 3차원 입체 조형물의 탄성율을 저하시킨다. 한편, 하이드록실기가 6개를 초과하여 포함되는 폴리에테르 폴리올 화합물을 사용하면, 제조된 3차원 입체 조형물이 불충분한 신율 및 감소된 내습성을 가질 수 있다.The polyether polyol compound is used having three or more hydroxyl groups in one molecule, preferably three to six hydroxyl groups in one molecule. The polyether polyol compound having less than three hydroxyl groups in one molecule makes the photocurability of the photocurable resin composition for stereoscopic molding insufficient and lowers the elastic modulus of the prepared three-dimensional stereoscopic sculpture. On the other hand, if a polyether polyol compound containing more than 6 hydroxyl groups is used, the prepared 3D stereoscopic sculpture may have insufficient elongation and reduced moisture resistance.
상기 폴리에테르 폴리올 화합물의 구체적인 예로는, 트리메틸올프로판, 글리세롤, 펜타에리트리톨, 소르비톨, 수크로스 및 쿼드롤 등의 하이드록실기를 3개 이상 갖는 다가 알코올을 에틸렌 옥사이드(EO), 프로필렌 옥사이드(PO), 부틸렌 옥사이드 및 테트라하이드로퓨란 등의 환형 에테르 화합물로 개질시켜 수득한 폴리에테르 폴리올 화합물을 들 수 있다. Specific examples of the polyether polyol compound include polyhydric alcohols having three or more hydroxyl groups such as trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, and quadrol, ethylene oxide (EO), propylene oxide (PO). ), polyether polyol compounds obtained by modification with cyclic ether compounds such as butylene oxide and tetrahydrofuran.
구체적으로 예를 들면, EO로 개질된 트리메틸올프로판, PO로 개질된 트리메틸올프로판, 테트라하이드로퓨란으로 개질된 트리메틸올프로판, EO로 개질된 글리세롤, PO로 개질된 글리세롤, 테트라하이드로퓨란으로 개질된 글리세롤, EO로 개질된 펜타에리트리톨, PO로 개질된 펜타에리트리톨, 테트라하이드로퓨란으로 개질된 펜타에리트리톨, EO로 개질된 소르비톨, PO로 개질된 소르비톨, EO로 개질된 수크로스, PO로 개질된 수크로스, EO로 개질된 쿼드롤 및 PO로 개질된 쿼드롤 등을 들 수 있다. 이들 중, EO로 개질된 트리메틸올프로판, PO로 개질된 트리메틸올프로판, PO로 개질된 글리세롤 및 PO로 개질된 소르비톨을 폴리에테르 폴리올 화합물로 사용하는 것이 바람직하다.Specifically, for example, trimethylolpropane modified with EO, trimethylolpropane modified with PO, trimethylolpropane modified with tetrahydrofuran, glycerol modified with EO, glycerol modified with PO, modified with tetrahydrofuran Glycerol, EO-modified pentaerythritol, PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified Sucrose, quadrol modified with EO, and quadrol modified with PO. Among these, it is preferable to use EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerol, and PO-modified sorbitol as a polyether polyol compound.
상기 폴리에테르 폴리올 화합물의 분자량은 바람직하게는 100 내지 2,000이며, 보다 바람직하게는 160 내지 1,000이다. 폴리에테르 폴리올 화합물의 분자량이 100 미만이면, 생성된 입체 조형용 광경화성 수지 조성물로부터 적합한 형태 안정성 및 물리적 안정성을 갖는 3차원 입체 조형물을 수득하기 어렵다. 또한, 폴리에테르 폴리올의 분자량이 2,000을 초과하면 입체 조형용 광경화성 수지 조성물의 점도가 증가하게 되어 광경화된 입체 조형물의 탄성율이 감소된다.The molecular weight of the polyether polyol compound is preferably 100 to 2,000, more preferably 160 to 1,000. If the molecular weight of the polyether polyol compound is less than 100, it is difficult to obtain a three-dimensional stereoscopic sculpture having suitable shape stability and physical stability from the resulting photocurable resin composition for stereoscopic molding. In addition, when the molecular weight of the polyether polyol exceeds 2,000, the viscosity of the photocurable resin composition for three-dimensional shaping increases, and the elastic modulus of the photo-cured three-dimensional sculpture decreases.
또한, 상기 폴리올 화합물을 입체 조형용 광경화성 수지 조성물에 사용할 경우, 상기 폴리올 화합물은 입체 조형용 광경화성 수지 조성물 총 중량에 대하여, 5 내지 35 중량%, 바람직하게는 5 내지 20 중량%, 보다 바람직하게는 5 내지 15 중량%로 포함된다. 상기 범위에서 본 발명의 입체 조형용 광경화성 수지 조성물의 광경화성이 충분하게 개선되는 효과를 얻을 수 있다. 또한, 양호한 형태 안정성 및 물리적 안정성을 갖는 입체 조형물을 파괴 없이 수득할 수 있다.
In addition, when the polyol compound is used in a photocurable resin composition for stereoscopic shaping, the polyol compound is 5 to 35% by weight, preferably 5 to 20% by weight, more preferably, based on the total weight of the photocurable resin composition for stereoscopic shaping It is included in 5 to 15% by weight. In the above range, the effect of sufficiently improving the photocurability of the photocurable resin composition for three-dimensional shaping of the present invention can be obtained. Further, a three-dimensional sculpture having good shape stability and physical stability can be obtained without destruction.
본 발명의 입체 조형용 광경화성 수지 조성물에는, 본 발명의 목적 및 효과를 손상시키지 않는 범위 내에서, 그 밖의 임의적 성분으로서 다양한 첨가제를 포함할 수 있으며, 사용될 수 있는 첨가제로는 용매, 중합 금지제, 레벨링제, 계면활성제, 가소제, 산화방지제, 자외선 흡수제, 대전 방지제, 난연제, 난연조제, 충전제, 안료 및 염료 등의 각종 첨가제를 포함할 수 있다.
The photocurable resin composition for three-dimensional shaping of the present invention may contain various additives as other optional components within a range not impairing the object and effect of the present invention, and additives that can be used include solvents, polymerization inhibitors, Various additives such as leveling agents, surfactants, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, flame retardants, fillers, pigments and dyes may be included.
본 발명의 입체 조형용 광경화성 수지 조성물은 광을 조사하여 특정 부분을 경화시킨 후, 경화층 위에 다시 상기 입체 조형용 광경화성 수지 조성물을 적층하고 광경화하는 과정을 반복하여 입체 형상의 조형물을 얻을 수 있다.In the three-dimensional molding photocurable resin composition of the present invention, after curing a specific portion by irradiating light, the above-described three-dimensional molding photocurable resin composition is laminated on the cured layer again, and the process of photocuring is repeated to obtain a three-dimensional sculpture. .
보다 자세하게는 스테레오리소그래피 장치로 3차원 입체 조형물을 제조하기 위해 사용되는 일반적인 절차는 다음과 같다. 입체 조형용 광경화성 수지 조성물의 표면 전체 또는 예정된 패턴에 UV/vis 광원을 조사하여, 원하는 두께의 층을 조사된 영역에서 경화시키고, 입체 조형용 광경화성 수지 조성물의 새로운 층을 상기 경화된 층 위에 형성시킨다. 또한, 새로운 층을 표면 전체 또는 예정된 패턴에 UV/vis 광원을 조사하여 새롭게 경화된 층을 경화된 층 상부에 접착시킨다. 상기 동일한 과정으로 층 형성 및 광 조사를 하여 층을 순차적으로 형성 및 적층한다. 최종 적층이 완료된 3차원 입체 조형물의 표면에 부착되는 입체 조형용 광경화성 수지 조성물은 세정 또는 기타 기법에 의해 제거한다. 또한, 필요한 경우 3차원 입체 조형물은 UV 램프 광으로 조사 또는 가열되어 후 경화를 더 진행 시킬 수 있다. 상기 방식으로 수득된 3차원 입체 조형물은 굴곡 탄성율 및 내충격성 등 높은 기계적 특성을 갖는다.
In more detail, a general procedure used to manufacture a 3D stereoscopic object with a stereolithography apparatus is as follows. By irradiating a UV/vis light source on the entire surface or a predetermined pattern of the three-dimensional shaping photocurable resin composition, a layer of a desired thickness is cured in the irradiated area, and a new layer of the three-dimensional shaping photocurable resin composition is formed on the cured layer. . In addition, the new layer is irradiated with a UV/vis light source on the entire surface or a predetermined pattern to adhere the newly cured layer on the cured layer. Layer formation and light irradiation are performed in the same process as described above to sequentially form and stack layers. The photocurable resin composition for three-dimensional molding attached to the surface of the three-dimensional three-dimensional sculpture on which the final lamination has been completed is removed by washing or other techniques. In addition, if necessary, the three-dimensional sculpture can be further cured after being irradiated or heated with UV lamp light. The three-dimensional three-dimensional sculpture obtained in the above manner has high mechanical properties such as flexural modulus and impact resistance.
이하, 실시예 및 실험예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예 및 실험예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예 및 실험예에 의하여 한정되는 것은 아니다. 하기의 실시예 및 실험예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail through examples and experimental examples. However, the following examples and experimental examples are intended to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples and experimental examples. The following Examples and Experimental Examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
<입체 조형용 <Three-dimensional molding 광경화성Photocurable 수지 조성물의 제조> Preparation of resin composition>
실시예Example 1 내지 5 및 1 to 5 and 비교예Comparative example 1 내지 4. 1 to 4.
하기 표 1의 조성으로 실시예 및 비교예의 입체 조형용 광경화성 수지 조성물을 제조하였다.The photocurable resin composition for three-dimensional shaping of Examples and Comparative Examples was prepared with the composition of Table 1 below.
광개시제Cationic
Photoinitiator
단량체(Meth)acrylic
Monomer
에폭시 수지 : 3,4-에폭시시클로헥실메틸-3,4-에폭시시클로헥산카르복실레이트 "CelloxideTM 2021P" (다이셀 가가꾸 고교(주) 제조)Epoxy resin: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate "Celloxide TM 2021P" (manufactured by Daicel Chemical Industries, Ltd.)
옥세탄수지 : 비스{[1-에틸(3-옥세타닐)]메틸}에테르 "OXT-221" (토아고세이 캄파니 리미티드 제조)Oxetane resin: Bis{[1-ethyl(3-oxetanyl)]methyl}ether "OXT-221" (manufactured by Toagosei Co., Ltd.)
폴리올 : PO로 개질된 트리메틸올프로판 "선닉스 GP-400" (산요 케미칼 인더스트리즈 리미티드 제조)Polyol: Trimethylolpropane modified with PO "Sunnyx GP-400" (manufactured by Sanyo Chemical Industries Limited)
양이온성 광개시제 : 트리아릴술포니움 헥사플루오로포스페이트염 혼합물 "UVI-6992" (The Dow Chemical Company 제조)Cationic photoinitiator: Triarylsulfonium hexafluorophosphate salt mixture "UVI-6992" (manufactured by The Dow Chemical Company)
(메타)아크릴계 단량체 : 펜타에리트리톨트리아크릴레이트 "M340" (미원상사 제조)(Meth)acrylic monomer: pentaerythritol triacrylate "M340" (manufactured by Miwon Corporation)
광라디컬 발생제 : 1-하이드록시-시클로헥실페닐케톤 "I-184" (Ciba Specialty Chemicals Inc 제조)Optical radical generator: 1-hydroxy-cyclohexylphenylketone "I-184" (manufactured by Ciba Specialty Chemicals Inc)
액정형 고분자 : 폴리(옥시벤조에이트-디옥시바이페닐-테레프탈레이트) "S6000" (Sumitomo 제조)Liquid crystal polymer: poly(oxybenzoate-dioxybiphenyl-terephthalate) "S6000" (manufactured by Sumitomo)
가교제 1 : 화학식 1(SSC-2(Gunei Chemical Industry Co., Ltd. 제조))Crosslinking agent 1: Formula 1 (SSC-2 (manufactured by Gunei Chemical Industry Co., Ltd.))
가교제 2 : 화학식 2(SSC-3(Gunei Chemical Industry Co., Ltd. 제조))Crosslinking agent 2: Formula 2 (SSC-3 (manufactured by Gunei Chemical Industry Co., Ltd.))
가교제 3 : 화학식 3(SSC-1(Gunei Chemical Industry Co., Ltd. 제조))Crosslinking agent 3: Chemical formula 3 (SSC-1 (manufactured by Guneni Chemical Industry Co., Ltd.))
입자 : 알루미나 "AS-50" (덴키 화학공업 제조)
Particles: Alumina "AS-50" (manufactured by Denki Chemical Industries)
실험예Experimental example 1. 입체 조형물 제조 및 물성 측정 1. Three-dimensional sculpture manufacturing and measurement
초고속 광조형 시스템 SOLIFORM 500B(Teijin Seiki Co., Ltd)을 사용하여 상기 실시예 1 내지 5 및 비교예 1 내지 4의 입체 조형용 광경화성 수지 조성물을 상기 각각의 조성물의 표면에서 1000mW(파장 355nm)의 레이저 출력 및 적산광량 150mJ/cm2의 조건 하에서 0.1mm층 두께로 광학적 입체 조형을 반복적으로 수행하여 시편을 제조하였다.
Using the ultra-high-speed stereolithography system SOLIFORM 500B (Teijin Seiki Co., Ltd), the photocurable resin compositions for three-dimensional shaping of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared at 1000 mW (wavelength 355 nm) on the surface of each composition. Specimens were prepared by repeatedly performing optical three-dimensional shaping with a 0.1 mm layer thickness under the conditions of laser output and accumulated light intensity of 150 mJ/cm 2 .
1. 열변형 온도1. Heat deflection temperature
상기 각각의 시편(JIS K-7171에 준거한 바 형상)에 HDT 테스터 3M-2(Toyo Seiki Seisaku-Sho, Ltd.)를 사용하여 0.45MPa의 하중을 가하고, JIS K-7207(B법)에 준거하여, 시편의 열변형 온도를 측정하여, 결과를 하기 표 2에 나타내었다.
A load of 0.45 MPa was applied to each of the above specimens (bar shape in accordance with JIS K-7171) using HDT tester 3M-2 (Toyo Seiki Seisaku-Sho, Ltd.), and JIS K-7207 (method B) was applied. In accordance with the measurement, the heat distortion temperature of the specimen was measured, and the results are shown in Table 2 below.
2. 인장 시험2. Tensile test
상기 각각의 시편(JIS K-7113에 준거한 덤벨 형상)을 UTM 5567(INSTRON Corporation)를 사용하여 JIS K-7113에 따라 각각의 시편의 인장 강도 및 인장 탄성율를 측정하여, 그 결과를 하기 표 2에 나타내었다.
The tensile strength and tensile modulus of each specimen were measured according to JIS K-7113 using UTM 5567 (INSTRON Corporation) for each of the specimens (dumbbell shape in accordance with JIS K-7113), and the results are shown in Table 2 below. Indicated.
3. 3. 아이조도Izodo 충격강도 Impact strength
상기 각각의 시편(JIS K-7110에 준거한 바 형상)을 아이조도 충격강도 측정기 DG-1B2(Toyo Seiki Seisaku-Sho, Ltd.)를 사용하여 각각의 시편의 아이조도 충격강도를 측정하여, 그 결과를 하기 표 2에 나타내었다.
Each of the above specimens (bar shape in accordance with JIS K-7110) was measured for the Izodo impact strength of each specimen using an Izodo impact strength meter DG-1B2 (Toyo Seiki Seisaku-Sho, Ltd.), and the The results are shown in Table 2 below.
(0.45MPa부하)Heat deflection temperature (℃)
(0.45 MPa load)
상기 표 2의 결과에서, 실시예 1 내지 5의 액정형 고분자 및 가교제를 포함하는 본 발명의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물은 열변형 온도가 높으며, 인장강도, 인장탄성률 및 아이조도 충격강도가 모두 높은 값을 나타내어, 강성 및 인성이 우수하다는 것을 알 수 있었다.In the results of Table 2, the three-dimensional sculpture made of the photocurable resin composition for three-dimensional molding of the present invention containing the liquid crystal polymer and crosslinking agent of Examples 1 to 5 has a high heat deformation temperature, tensile strength, tensile modulus, and Izo degree. Both of the impact strengths showed high values, and it was found that the rigidity and toughness were excellent.
그러나, 상기 액정형 고분자 및 가교제를 포함하지 않은 비교예 1 내지 2의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물은 낮은 열변형 온도, 인장강도, 인장탄성률 및 아이조도 충격강도를 나타냈다.However, the three-dimensional sculptures made of the photocurable resin composition for three-dimensional molding of Comparative Examples 1 to 2 that did not contain the liquid crystal polymer and the crosslinking agent exhibited low thermal deformation temperature, tensile strength, tensile modulus, and Izodo impact strength.
또한, 액정형 고분자는 포함하고, 가교제를 포함하지 않은 비교예 3의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물은 비교예 1 내지 2에 비하여 우수한 결과를 보였지만, 실시예 1 내지 5의 결과보다 좋지 못하였다. 또한, 인장탄성률은 비교적 양호한 결과를 보였으나, 열변형 온도, 인장강도 및 아이조도 충격강도의 결과가 불량하였다.In addition, the three-dimensional sculpture made of the photocurable resin composition for three-dimensional shaping of Comparative Example 3 that contains a liquid crystal polymer and does not contain a cross-linking agent showed superior results compared to Comparative Examples 1 to 2, but than the results of Examples 1 to 5 It wasn't good. In addition, the tensile modulus showed relatively good results, but the results of the thermal deformation temperature, tensile strength, and Izodo impact strength were poor.
또한, 액정형 고분자는 포함하지 않고, 가교제를 포함한 비교예 4의 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물은 경화성 성분과의 가교에 의한 기계적 강도는 개선되는 경향이나 내열특성인 열변형 온도에는 개선효과가 없는 것으로 나타났다.In addition, the three-dimensional sculpture made of the photocurable resin composition for three-dimensional molding of Comparative Example 4 that does not contain a liquid crystal polymer but contains a crosslinking agent tends to improve mechanical strength by crosslinking with a curable component, but is not subject to heat distortion temperature, which is a heat resistance property. There was no improvement effect.
상기 결과를 통하여, 입체 조형용 광경화성 수지 조성물로 액정형 고분자 및 가교제를 포함하면, 상기 입체 조형용 광경화성 수지 조성물로 제조된 입체 조형물의 기계적 특성이 우수하다는 것을 실험을 통하여 알 수 있었다.
Through the above results, it was found through an experiment that when a liquid crystal polymer and a crosslinking agent were included as a three-dimensional shaping photocurable resin composition, the three-dimensional sculpture made of the three-dimensional shaping photo-curable resin composition was excellent.
따라서, 상기 실험예 1의 결과를 통하여, 본 발명의 입체 조형용 광경화성 수지 조성물은 액정형 고분자 및 가교제를 포함함으로써, 매우 우수한 열적 안정성 및 기계적 강도를 나타내는 효과를 가질 수 있다.Therefore, through the results of Experimental Example 1, the photocurable resin composition for three-dimensional shaping of the present invention includes a liquid crystal polymer and a crosslinking agent, thereby exhibiting very excellent thermal stability and mechanical strength.
Claims (8)
상기 가교제는 하기 화학식 1 내지 3으로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 입체 조형용 광경화성 수지 조성물.
[화학식 1]
[화학식 2]
[화학식 3]
(상기 R은 수소 또는 메틸기이다.)It includes a cationic curable monomer, a cationic photoinitiator, a (meth)acrylic monomer, a photoradical generator, a liquid crystal polymer and a crosslinking agent,
The crosslinking agent is a three-dimensional shaping photocurable resin composition comprising at least one selected from the group consisting of the following Chemical Formulas 1 to 3.
[Formula 1]
[Formula 2]
[Formula 3]
(The R is hydrogen or a methyl group.)
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