JP7426187B2 - Photocurable composition for support materials for 3D printers and support materials for 3D printers - Google Patents
Photocurable composition for support materials for 3D printers and support materials for 3D printers Download PDFInfo
- Publication number
- JP7426187B2 JP7426187B2 JP2020047520A JP2020047520A JP7426187B2 JP 7426187 B2 JP7426187 B2 JP 7426187B2 JP 2020047520 A JP2020047520 A JP 2020047520A JP 2020047520 A JP2020047520 A JP 2020047520A JP 7426187 B2 JP7426187 B2 JP 7426187B2
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- JP
- Japan
- Prior art keywords
- mass
- support material
- meth
- photocurable composition
- acrylate
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 125
- 239000000203 mixture Substances 0.000 title claims description 94
- 239000000178 monomer Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 61
- -1 vinylphenyl group Chemical group 0.000 description 48
- 150000003839 salts Chemical class 0.000 description 21
- 238000001723 curing Methods 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 125000003010 ionic group Chemical group 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 159000000001 potassium salts Chemical class 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 150000003751 zinc Chemical class 0.000 description 6
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 3
- ZKFOEDSYSPDTEB-UHFFFAOYSA-N 2-prop-2-enoyloxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC(=O)C=C ZKFOEDSYSPDTEB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 150000001206 Neodymium Chemical class 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-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
- 239000006229 carbon black Substances 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000945 filler Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
- YRIOTLGRXFJRTJ-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)(COP(O)(=O)O)C1=CC=CC=C1 YRIOTLGRXFJRTJ-UHFFFAOYSA-N 0.000 description 1
- LHRBODAKTKAMRZ-UHFFFAOYSA-N (1-phenyl-2-phosphonooxyethyl) prop-2-enoate Chemical compound OP(O)(=O)OCC(OC(=O)C=C)C1=CC=CC=C1 LHRBODAKTKAMRZ-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- QGNDAXYFYSPDKJ-ZQFDHWOPSA-N (E)-3-hydroxy-2-[(4-methyl-2-nitrophenyl)diazenyl]-N-phenylbut-2-enamide Chemical compound C\C(O)=C(/N=NC1=CC=C(C)C=C1[N+]([O-])=O)C(=O)NC1=CC=CC=C1 QGNDAXYFYSPDKJ-ZQFDHWOPSA-N 0.000 description 1
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 description 1
- KGGVGTQEGGOZRN-PLNGDYQASA-N (nz)-n-butylidenehydroxylamine Chemical compound CCC\C=N/O KGGVGTQEGGOZRN-PLNGDYQASA-N 0.000 description 1
- KMZOJSINLAGOMV-UHFFFAOYSA-N (prop-2-enoylamino) propane-1-sulfonate Chemical compound CCCS(=O)(=O)ONC(=O)C=C KMZOJSINLAGOMV-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- AROCLDYPZXMJPW-UHFFFAOYSA-N 1-(octyldisulfanyl)octane Chemical compound CCCCCCCCSSCCCCCCCC AROCLDYPZXMJPW-UHFFFAOYSA-N 0.000 description 1
- GCRUYRFHWGPWHJ-UHFFFAOYSA-N 1-but-1-enoxybutane Chemical compound CCCCOC=CCC GCRUYRFHWGPWHJ-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- YVURAEQQLUQPFO-UHFFFAOYSA-N phosphoric acid;styrene Chemical compound OP(O)(O)=O.C=CC1=CC=CC=C1 YVURAEQQLUQPFO-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
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- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- 239000002964 rayon Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 229950011392 sorbitan stearate Drugs 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl 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])[H] 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、３Ｄプリンター用サポート材用光硬化性組成物ならびに３Ｄプリンター用サポート材に関する。 The present invention relates to a photocurable composition for a support material for a 3D printer and a support material for a 3D printer.
近年、インクジェットノズルから吐出した液状の光硬化性樹脂を硬化させ、積層して光造形するインクジェット方式による光造形法が提案されている。この光造形法を用いたインクジェット３Ｄプリンター用インクは、ＵＶ等の光硬化により成型体を構成するモデル材と、モデル材を立体的に積み上げる際の支持材として使用するサポート材とを含んでいる。サポート材の上にモデル材を積層することで、オーバーハング構造や中空構造を造形することが可能となる。 In recent years, an inkjet stereolithography method has been proposed in which a liquid photocurable resin discharged from an inkjet nozzle is cured and layered for stereolithography. The ink for an inkjet 3D printer using this stereolithography method includes a model material that forms a molded body by photocuring such as UV light, and a support material that is used as a support material when stacking the model materials three-dimensionally. . By layering model materials on top of support materials, it is possible to create overhang structures and hollow structures.
特許文献１には、エチレン重合性基を有する少なくとも２種類の単官能モノマーと光開始剤とを含有する３Ｄ造形用組成液であって、単官能モノマーとしてイオン性基を有する単官能モノマーおよびイオン性基を有しない単官能モノマーを含み、イオン性基の対イオンをさらに含有する３Ｄ造形用組成液と、サポート材組成液とを含む、３Ｄ造形用インクセットが記載されている。上記３Ｄ造形用組成液では、紫外線照射によって硬化させることができ、さらには高い靱性を有し、壊れにくい３Ｄ造形物が得られることが記載されている。 Patent Document 1 describes a 3D modeling composition liquid containing at least two types of monofunctional monomers having an ethylene polymerizable group and a photoinitiator, the monofunctional monomers including a monofunctional monomer having an ionic group and an ion. A 3D printing ink set is described that includes a 3D printing composition liquid containing a monofunctional monomer having no functional group and further containing a counter ion of an ionic group, and a support material composition liquid. It is described that the above-mentioned composition liquid for 3D modeling can be cured by ultraviolet irradiation, and furthermore, a 3D modeled object having high toughness and being hard to break can be obtained.
サポート材用光硬化性組成物には、さらに、造形後に外観に優れた造形物を与えることが求められている。 The photocurable composition for a support material is further required to provide a shaped article with an excellent appearance after being shaped.
従って、本発明の課題は、造形後に、外観に優れた造形物を与える、３Ｄプリンター用サポート材用光硬化性組成物ならびに３Ｄプリンター用サポート材を提供することにある。 Therefore, an object of the present invention is to provide a photocurable composition for a support material for a 3D printer and a support material for a 3D printer, which give a molded object with an excellent appearance after modeling.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、所定の単量体を所定の配合で有し、水の含有量が少なく、所定のｐＨを有する、３Ｄプリンター用サポート材用光硬化性組成物ならびに３Ｄプリンター用サポート材により、上記課題が解決できることを見出し、本発明を完成するに至った。 As a result of extensive research to solve the above problems, the present inventors have discovered a support for 3D printers that has a specific monomer in a specific formulation, has a low water content, and has a specific pH. We have discovered that the above problems can be solved by a photocurable composition for materials and a support material for 3D printers, and have completed the present invention.
すなわち、本発明の３Ｄプリンター用サポート材用光硬化性組成物では、イオン性水溶性単量体を１０質量％～８０質量％含み、非イオン性水溶性単量体を５質量％～５０質量％含み、非イオン性非水溶性単量体を０質量％～５０質量％含み、水の含有量が１．０質量％以下であり、ｐＨが５～８である。
また、本発明の３Ｄプリンター用サポート材は、濁度が４０％未満である。
That is, the photocurable composition for a support material for a 3D printer of the present invention contains 10% by mass to 80% by mass of an ionic water-soluble monomer, and 5% by mass to 50% by mass of a nonionic water-soluble monomer. %, contains 0% to 50% by mass of a nonionic water-insoluble monomer, has a water content of 1.0% by mass or less, and has a pH of 5 to 8.
Further, the support material for a 3D printer of the present invention has a turbidity of less than 40%.
本発明の３Ｄプリンター用サポート材用光硬化性組成物ならびに３Ｄプリンター用サポート材によれば、モデル材をサポートする硬さと、溶剤への優れた溶解性を両立したインクジェット３Ｄプリンター用サポート材の製造方法、サポート材、及び光造形物の製造方法を提供できる。 According to the photocurable composition for a support material for a 3D printer and the support material for a 3D printer of the present invention, a support material for an inkjet 3D printer that has both hardness to support a model material and excellent solubility in a solvent can be produced. A method, a support material, and a method for manufacturing a stereolithographic object can be provided.
［３Ｄプリンター用サポート材用光硬化性組成物］
本発明の３Ｄプリンター用サポート材用光硬化性組成物（以下、単にサポート材用光硬化性組成物という場合がある）では、イオン性水溶性単量体を１０質量％～８０質量％含み、非イオン性水溶性単量体を５質量％～５０質量％含み、非イオン性非水溶性単量体を０質量％～５０質量％含み、水の含有量が１．０質量％以下であり、ｐＨが５～８である。
[Photocurable composition for support material for 3D printer]
The photocurable composition for a support material for a 3D printer of the present invention (hereinafter sometimes simply referred to as a photocurable composition for a support material) contains 10% by mass to 80% by mass of an ionic water-soluble monomer, Contains 5% to 50% by mass of a nonionic water-soluble monomer, 0% to 50% by mass of a nonionic water-insoluble monomer, and has a water content of 1.0% by mass or less. , pH is 5-8.
（イオン性水溶性単量体）
本発明の３Ｄプリンター用サポート材用光硬化性組成物に含まれるイオン性水溶性単量体は、イオン性基と対イオンとを含有し、好ましくは水溶解度（２０℃）が２０ｇ／Ｌ以上である単量体である。上記イオン性水溶性単量体としては、エチレン性不飽和基を分子内に１つ以上有し、イオン性基と対イオンとを含有する水溶性エチレン性不飽和単量体が好ましい。イオン性基と対イオンとを含有する水溶性エチレン性不飽和単量体は、イオン性基と対イオンとを含有することにより、水溶性が高い。水溶解度（２０℃）は、１００ｇ／Ｌ以上であることが好ましく、２００ｇ／Ｌ以上であることがより好ましく、５００ｇ／Ｌ以上であることがさらに好ましい。
(ionic water-soluble monomer)
The ionic water-soluble monomer contained in the photocurable composition for a support material for a 3D printer of the present invention contains an ionic group and a counter ion, and preferably has a water solubility (at 20°C) of 20 g/L or more. It is a monomer that is The ionic water-soluble monomer is preferably a water-soluble ethylenically unsaturated monomer that has one or more ethylenically unsaturated groups in its molecule and contains an ionic group and a counter ion. The water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion has high water solubility because it contains an ionic group and a counter ion. The water solubility (at 20° C.) is preferably 100 g/L or more, more preferably 200 g/L or more, and even more preferably 500 g/L or more.
エチレン性不飽和基としては、エチレン基、プロペニル基、ブテニル基、ビニルフェニル基、（メタ）アクリル基、アリルエーテル基、ビニルエーテル基、マレイル基、マレイミド基、(メタ）アクリルアミド基、アセチルビニル基およびビニルアミド基などが挙げられる。なお、本明細書において、「（メタ）アクリル」は「アクリル」、「メタクリル」の双方又は何れかを意味し、「（メタ）アクリレート」は「アクリレート」、「メタクリレート」の双方又は何れかを意味する。なかでも、（メタ）アクリル基、ビニルエーテル基および（メタ）アクリルアミド基が好ましく、（メタ）アクリル基がより好ましい。 Ethylenically unsaturated groups include ethylene group, propenyl group, butenyl group, vinylphenyl group, (meth)acrylic group, allyl ether group, vinyl ether group, maleyl group, maleimide group, (meth)acrylamide group, acetylvinyl group, and Examples include vinylamide groups. In this specification, "(meth)acrylic" means "acrylic" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate". means. Among these, (meth)acrylic group, vinyl ether group and (meth)acrylamide group are preferred, and (meth)acrylic group is more preferred.
上記イオン性基としては、カルボン酸、リン酸、スルホン酸等が挙げられる。中でもカルボン酸が好ましい。 Examples of the ionic group include carboxylic acid, phosphoric acid, and sulfonic acid. Among them, carboxylic acids are preferred.
上記対イオンとしては、ナトリウムイオン、カリウムイオン、アンモニウムイオン等の１価の対イオン；亜鉛イオン、マグネシウムイオン、カルシウムイオン、アルミニウムイオン、ネオジウムイオン等の多価の金属イオンなどが挙げられる。中でも、１価の対イオンが好ましく、ナトリウムイオン、カリウムイオン、またはアンモニウムイオンがより好ましく用いられ、さらに好ましくはカリウムイオンが用いられる。１価の対イオンに加えて、亜鉛イオン、マグネシウムイオン、カルシウムイオン、アルミニウムイオン、またはネオジウムイオンなどの多価の金属イオンを用いることも好ましい。 Examples of the counter ions include monovalent counter ions such as sodium ions, potassium ions, and ammonium ions; polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, and neodymium ions. Among these, monovalent counter ions are preferred, sodium ions, potassium ions, or ammonium ions are more preferred, and potassium ions are even more preferred. In addition to monovalent counterions, it is also preferred to use polyvalent metal ions such as zinc ions, magnesium ions, calcium ions, aluminum ions, or neodymium ions.
対イオンとして、１価の対イオンを含有する水溶性エチレン性不飽和単量体と、多価の金属イオンを含有する水溶性エチレン性不飽和単量体とを併用した場合に、サポート材用光硬化性組成物を光硬化して得られる硬化物のサポート性をより向上できる。また、これらに加えて、さらに後述の有機酸及び／又はその塩と併用することは本発明の好ましい形態である。多価金属イオンで好ましくは、亜鉛イオン、マグネシウムイオン、カルシウムイオンである。
なお、本明細書において、サポート性（サポート力）とは、サポート材用光硬化性組成物の硬化物がモデル材の硬化物を支える性能であり、後述する方法で測定される、サポート材の硬化物の硬度（ショワＥ）で表すことができる。
When a water-soluble ethylenically unsaturated monomer containing a monovalent counter ion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion are used together as counter ions, The support properties of the cured product obtained by photocuring the photocurable composition can be further improved. Moreover, in addition to these, it is a preferable form of the present invention to use together with an organic acid and/or a salt thereof, which will be described later. Preferred polyvalent metal ions are zinc ion, magnesium ion, and calcium ion.
In addition, in this specification, the support property (supporting force) is the ability of the cured product of the photocurable composition for support material to support the cured product of the model material, and is the ability of the cured product of the photocurable composition for support material to support the cured product of the support material, which is measured by the method described below. It can be expressed by the hardness (Shower E) of the cured product.
上記サポート材用光硬化性組成物中に含まれるイオン性水溶性単量体の含有量としては、上記組成物１００質量％中、上限としては８０質量％以下、好ましくは６０質量％以下、より好ましくは５０質量％以下、さらに好ましくは４０質量％以下であり、下限としては１０質量％以上、好ましくは２０質量％以上、より好ましくは２５質量％以上、さらに好ましくは３０質量％以上である。このようにした場合に、該サポート材用光硬化性組成物を用いて造形後に、外観に優れた造形物が製造される。 The content of the ionic water-soluble monomer contained in the photocurable composition for support material is up to 80% by mass, preferably 60% by mass or less, based on 100% by mass of the composition. Preferably it is 50% by mass or less, more preferably 40% by mass or less, and the lower limit is 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more. In this case, after modeling using the photocurable composition for support material, a shaped article with excellent appearance is manufactured.
上記サポート材用光硬化性組成物中に含まれるイオン性基と対イオンとを含有する水溶性エチレン性不飽和単量体の含有量としては、上記組成物１００質量％中、上限としては８０質量％以下、好ましくは６０質量％以下、より好ましくは５０質量％以下、さらに好ましくは４０質量％以下であり、下限としては１０質量％以上、好ましくは２０質量％以上、より好ましくは２５質量％以上、さらに好ましくは３０質量％以上である。このようにした場合に、該サポート材用光硬化性組成物を用いて造形後に、外観に優れた造形物が製造される。 The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion in the photocurable composition for support materials is 80% by mass in 100% by mass of the composition. % by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and the lower limit is 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass. The content is more preferably 30% by mass or more. In this case, after modeling using the photocurable composition for support material, a shaped article with excellent appearance is manufactured.
対イオンとして１価の対イオンを含有する水溶性エチレン性不飽和単量体と、対イオンとして多価の金属イオンを含有する水溶性エチレン性不飽和単量体と、の合計含有量としては、サポート材用光硬化性組成物１００質量％中、上限としては８０質量％以下、好ましくは６０質量％以下、より好ましくは５０質量％以下、さらに好ましくは４０質量％以下であり、下限としては１０質量％以上、好ましくは２０質量％以上、より好ましくは２５質量％以上、さらに好ましくは３０質量％以上である。 The total content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion as a counterion and the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is In 100% by mass of the photocurable composition for support material, the upper limit is 80% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and the lower limit is The content is 10% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
対イオンとして１価の対イオンを含有する水溶性エチレン性不飽和単量体の含有量は、サポート材用光硬化性組成物１００質量％中、上限としては、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３５質量％以下であり、下限としては、好ましくは１０質量％以上、より好ましくは１３質量％以上、さらに好ましくは１５質量％以上である。
上記のようにした場合にサポート材用光硬化性組成物のサポート性とともに溶解性をより向上できる。
The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing a monovalent counterion is preferably 50% by mass or less, based on 100% by mass of the photocurable composition for support material. Preferably it is 40% by mass or less, more preferably 35% by mass or less, and the lower limit is preferably 10% by mass or more, more preferably 13% by mass or more, and still more preferably 15% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.
対イオンとして多価の金属イオンを含有する水溶性エチレン性不飽和単量体の含有量は、サポート材用光硬化性組成物１００質量％中、上限としては、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下であり、下限としては、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上である。
上記のようにした場合にサポート材用光硬化性組成物のサポート性とともに溶解性をより向上できる。
The upper limit of the content of the water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion as a counterion is preferably 40% by mass or less, based on 100% by mass of the photocurable composition for support material. Preferably it is 30% by mass or less, more preferably 20% by mass or less, and the lower limit is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.
上記サポート材用光硬化性組成物に含まれる、イオン性基としてのカルボン酸と対イオンとを含有する水溶性エチレン性不飽和単量体としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、２－（メタ）アクリロイルオキシ安息香酸、３－（メタ）アクリロイルオキシ安息香酸、４－（メタ）アクリロイルオキシ安息香酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルコハク酸、２－ビニル安息香酸、３－ビニル安息香酸、４－ビニル安息香酸、Ｎ－（メタ）アクリロイルアスパラギン酸、ω－（メタ）アクロイルアルカン－１，１ジカルボン酸類の、ナトリウム塩、カリウム塩等のアルカリ金属塩及びアンモニウム塩等の１価塩；亜鉛塩、マグネシウム塩、カルシウム塩、アルミニウム塩、またはネオジウム塩等の多価塩などが挙げられる。
中でも、ナトリウム塩、カリウム塩等のアルカリ金属塩及びアンモニウム塩等の１価塩が好ましく、より好ましくはナトリウム塩、カリウム塩又はアンモニウム塩である。さらに好ましくはカリウム塩である。
Examples of water-soluble ethylenically unsaturated monomers containing carboxylic acid as an ionic group and counter ions included in the photocurable composition for support materials include acrylic acid, methacrylic acid, maleic acid, and fumaric acid. , 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth) Acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, N-(meth)acryloyl aspartic acid, ω-(meth) Monovalent salts such as alkali metal salts such as sodium salts and potassium salts and ammonium salts of acroylalkane-1,1 dicarboxylic acids; polyvalent salts such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts Examples include.
Among these, alkali metal salts such as sodium salts and potassium salts and monovalent salts such as ammonium salts are preferred, and sodium salts, potassium salts, and ammonium salts are more preferred. More preferred is potassium salt.
カルボン酸の１価塩と多価金属塩を併用した場合に、サポート材用光硬化性組成物を光硬化して得られる硬化物のサポート性をより向上できる。また、これらに加えて、さらに後述の有機酸及び／又はその塩と併用することは本発明の好ましい形態である。カルボン酸多価金属塩で好ましくは、亜鉛塩、マグネシウム塩、カルシウム塩である。 When a monovalent salt of a carboxylic acid and a polyvalent metal salt are used together, the support properties of a cured product obtained by photocuring a photocurable composition for a support material can be further improved. Moreover, in addition to these, it is a preferable form of the present invention to use together with an organic acid and/or a salt thereof, which will be described later. Among the polyvalent metal carboxylic acid salts, preferred are zinc salts, magnesium salts, and calcium salts.
カルボン酸の１価塩と多価金属塩の合計含有量としては、サポート材用光硬化性組成物１００質量％中、上限としては８０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下であり、下限としては好ましくは２０質量％以上、より好ましくは２５質量％以上、さらに好ましくは３０質量％以上である。 The total content of monovalent carboxylic acid salts and polyvalent metal salts is up to 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less in 100% by mass of the photocurable composition for support material. The lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
カルボン酸の１価塩の含有量は、サポート材用光硬化性組成物１００質量％中、上限としては、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３５質量％以下であり、下限としては、好ましくは１０質量％以上、より好ましくは１３質量％以上、さらに好ましくは１５質量％以上である。 The upper limit of the content of the monovalent salt of carboxylic acid in 100% by mass of the photocurable composition for support material is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 13% by mass or more, even more preferably 15% by mass or more.
カルボン酸の多価金属塩の含有量は、サポート材用光硬化性組成物１００質量％中、上限としては、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下であり、下限としては、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上である。
上記のようにした場合に、サポート材用光硬化性組成物のサポート性とともに溶解性をより向上できる。
The content of the polyvalent metal salt of carboxylic acid is preferably at most 40% by mass, more preferably at most 30% by mass, even more preferably at most 20% by mass, based on 100% by mass of the photocurable composition for support material. The lower limit is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.
イオン性基としてのカルボン酸と対イオンとを含有する水溶性エチレン性不飽和単量体としては、カルボン酸に含まれる炭素数が３～１５のナトリウム塩、カリウム塩、亜鉛塩、及びカルシウム塩が好ましく、炭素数３～１２のナトリウム塩、カリウム塩、亜鉛塩、及びカルシウム塩がより好ましい。上記炭素数としては、炭素数３～９がより好ましく、炭素数３～６がさらに好ましい。中でも、（メタ）アクリル酸カリウム、（メタ）アクリル酸ナトリウム、（メタ）アクリル酸亜鉛、（メタ）アクリル酸カルシウムが特に好ましい。炭素数が少ない単量体を用いることにより、分子中の疎水性部分を小さくすることができ、水溶性エチレン性不飽和単量体の水溶性をより高められる。 Examples of water-soluble ethylenically unsaturated monomers containing carboxylic acid as an ionic group and a counter ion include sodium salts, potassium salts, zinc salts, and calcium salts containing 3 to 15 carbon atoms in the carboxylic acid. are preferred, and sodium salts, potassium salts, zinc salts, and calcium salts having 3 to 12 carbon atoms are more preferred. The number of carbon atoms is more preferably 3 to 9 carbon atoms, and even more preferably 3 to 6 carbon atoms. Among these, potassium (meth)acrylate, sodium (meth)acrylate, zinc (meth)acrylate, and calcium (meth)acrylate are particularly preferred. By using a monomer with a small number of carbon atoms, the hydrophobic portion in the molecule can be made small, and the water solubility of the water-soluble ethylenically unsaturated monomer can be further increased.
上記サポート材用光硬化性組成物に含まれる、イオン性基としてのリン酸と対イオンとを含有する水溶性エチレン性不飽和単量体としては、例えば、モノ（２－アクリロイルオキシエチル）アシッドホスフェート、モノ（２－メタクリロイルオキシエチル）アシッドホスフェート、ジフェニル（２－アクリロイルオキシエチル）ホスフェート、ジフェニル（２－メタクリロイルオキシエチル）ホスフェート、フェニル（２－アクリロイルオキシエチル）ホスフェート、アシッドホスホオキシエチルメタクリレート、メタクロイルオキシエチルアシッドホスフェート、ホスホオキシポリオキシエチレングリコールモノメタクリレート、アシッド・ホスホオキシポリオキシプロピレングリコールメタクリレート、（メタ）アクリロイルオキシエチルアシッドホスフェート、（メタ）アクリロイルオキシプロピルアシッドホスフェート、（メタ）アクリロイルオキシ－２－ヒドロキシプロピルアシッドホスフェート、（メタ）アクリロイルオキシ－３－ヒドロキシプロピルアシッドホスフェート、（メタ）アクリロイルオキシ－３－クロロ－２－ヒドロキシプロピルアシッドホスフェート、ならびにビニルリン酸、ｐ－ビニルベンゼンリン酸等の分子内にホスホノ基を有する化合物の、ナトリウム塩、カリウム塩、及びアンモニウム塩が挙げられる。 Examples of the water-soluble ethylenically unsaturated monomer containing phosphoric acid as an ionic group and a counter ion included in the photocurable composition for support materials include mono(2-acryloyloxyethyl) acid. Phosphate, mono(2-methacryloyloxyethyl) acid phosphate, diphenyl(2-acryloyloxyethyl) phosphate, diphenyl(2-methacryloyloxyethyl) phosphate, phenyl(2-acryloyloxyethyl) phosphate, acid phosphooxyethyl methacrylate, methacrylate yloxyethyl acid phosphate, phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol methacrylate, (meth)acryloyloxyethyl acid phosphate, (meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxy-2 -Hydroxypropyl acid phosphate, (meth)acryloyloxy-3-hydroxypropyl acid phosphate, (meth)acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, as well as vinyl phosphoric acid, p-vinylbenzene phosphate, etc. Examples include sodium salts, potassium salts, and ammonium salts of compounds having a phosphono group.
上記サポート材用光硬化性組成物に含まれる、イオン性基としてのスルホン酸と対イオンとを含有する水溶性エチレン性不飽和単量体としては、例えば、アリルスルホン酸、イソプレンスルホン酸、２－（メタ）アクリルアミドエチルスルホン酸、３－（メタ）アクリルアミドプロピルスルホン酸、４－（メタ）アクリルアミドブチルスルホン酸、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、ｐ－ビニルベンゼンスルホン酸、およびビニルスルホン酸等の化合物の、ナトリウム塩、カリウム塩、及びアンモニウム塩が挙げられる。上記例示のイオン性基と対イオンとを含有する水溶性エチレン性不飽和単量体は、単独で用いてもよいし、２種以上を組み合わせて使用してもよい。 Examples of the water-soluble ethylenically unsaturated monomer containing sulfonic acid as an ionic group and a counter ion included in the photocurable composition for support materials include allyl sulfonic acid, isoprene sulfonic acid, -(meth)acrylamidoethylsulfonic acid, 3-(meth)acrylamidopropylsulfonic acid, 4-(meth)acrylamidobutylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and sodium, potassium, and ammonium salts of compounds such as vinyl sulfonic acid. The above-exemplified water-soluble ethylenically unsaturated monomers containing an ionic group and a counter ion may be used alone or in combination of two or more.
上記サポート材用光硬化性組成物中に含まれる水溶性エチレン性不飽和単量体としては、アクリル酸塩が好ましく、リチウム、ナトリウム、カリウム等のアルカリ金属塩、アンモニウム塩、アミン塩等、アクリル酸の１価塩がより好ましく、さらに好ましくはアルカリ金属塩又はアンモニウム塩、特に好ましくはナトリウム塩、カリウム塩又はアンモニウム塩である。最も好ましくはカリウム塩である。 The water-soluble ethylenically unsaturated monomer contained in the photocurable composition for support material is preferably acrylate, and alkali metal salts such as lithium, sodium, and potassium, ammonium salts, amine salts, etc., acrylic salts, etc. More preferred are monovalent salts of the acid, even more preferred are alkali metal salts or ammonium salts, particularly preferred are sodium salts, potassium salts or ammonium salts. Most preferred are potassium salts.
上記サポート材用光硬化性組成物中に含まれる水溶性エチレン性不飽和単量体としては、上記に加えて、亜鉛塩、マグネシウム塩、カルシウム塩、アルミニウム塩、またはネオジウム塩等のアクリル酸多価金属塩を含んでいてもよい。アクリル酸多価金属塩で好ましくは、亜鉛塩、マグネシウム塩、カルシウム塩である。 In addition to the above, water-soluble ethylenically unsaturated monomers contained in the photocurable composition for support materials include acrylic acid monomers such as zinc salts, magnesium salts, calcium salts, aluminum salts, or neodymium salts. It may also contain a valent metal salt. Among the polyvalent metal salts of acrylic acid, preferred are zinc salts, magnesium salts, and calcium salts.
アクリル酸の１価塩と多価金属塩を併用した場合に、サポート材用光硬化性組成物を光硬化して得られる硬化物のサポート性をより向上できる。アクリル酸の１価塩と多価金属塩を併用する組み合わせとしては、アクリル酸カリウムとアクリル酸亜鉛の組み合わせが好ましい。アクリル酸亜鉛を併用することにより、より高い強度の硬化物を得ることができる。 When a monovalent salt of acrylic acid and a polyvalent metal salt are used together, the support properties of a cured product obtained by photocuring a photocurable composition for a support material can be further improved. As a combination of a monovalent salt of acrylic acid and a polyvalent metal salt, a combination of potassium acrylate and zinc acrylate is preferred. By using zinc acrylate in combination, a cured product with higher strength can be obtained.
アクリル酸の１価塩と多価金属塩の合計含有量としては、サポート材用光硬化性組成物１００質量％中、上限としては８０質量％以下、好ましくは７０質量％以下、より好ましくは６０質量％以下であり、下限としては好ましくは２０質量％以上、より好ましくは２５質量％以上、さらに好ましくは３０質量％以上である。
中でも、アクリル酸カリウムとアクリル酸亜鉛の合計含有量が、サポート材用光硬化性組成物１００質量％中、３０～６０質量％であることが好ましい。
上記のようにした場合にサポート材用光硬化性組成物のサポート性とともに溶解性をより向上できる。
The total content of monovalent salts and polyvalent metal salts of acrylic acid is up to 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass in 100% by mass of the photocurable composition for support material. The lower limit is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more.
Among these, the total content of potassium acrylate and zinc acrylate is preferably 30 to 60% by mass based on 100% by mass of the photocurable composition for support material.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.
また、アクリル酸の１価塩の含有量は、上限としては、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３５質量％以下であり、下限としては、好ましくは１０質量％以上、より好ましくは１３質量％以上、さらに好ましくは１５質量％以上である。
アクリル酸の多価金属塩の含有量は、上限としては、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２０質量％以下であり、下限としては、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上である。
上記のようにした場合にサポート材用光硬化性組成物のサポート性とともに溶解性をより向上できる。
Further, the upper limit of the content of the monovalent salt of acrylic acid is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and the lower limit is preferably 10% by mass or less. % or more, more preferably 13% by mass or more, still more preferably 15% by mass or more.
The upper limit of the content of the polyvalent metal salt of acrylic acid is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and the lower limit is preferably 5% by mass. The content is more preferably 8% by mass or more, and even more preferably 10% by mass or more.
In the case described above, the support properties and solubility of the photocurable composition for support material can be further improved.
（非イオン性水溶性単量体）
上記イオン性水溶性単量体以外の非イオン性水溶性単量体としては、（メタ）アクリル酸；アクリロイルモルホリン；Ｎ－ビニルピロリドン；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、２Ｎ－イソプロピルアクリルアミド等のアクリルアミド、メトキシトリエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、２－（２－エトキシエトキシ）エチル（メタ）アクリレート、グリセロール（メタ）アクリレート、ポリエチレングリコールアクリレート等が挙げられる。
(Nonionic water-soluble monomer)
Nonionic water-soluble monomers other than the above-mentioned ionic water-soluble monomers include (meth)acrylic acid; acryloylmorpholine; N-vinylpyrrolidone; (meth)acrylamide, N,N-dimethylacrylamide, N,N -Acrylamides such as diethylacrylamide, N-hydroxyethylacrylamide, 2N-isopropylacrylamide, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, glycerol ( Examples include meth)acrylate, polyethylene glycol acrylate, and the like.
非イオン性水溶性単量体の合計含有量としては、サポート材用光硬化性組成物１００質量％中、上限としては５０質量％以下、好ましくは４０質量％以下、より好ましくは３０質量％以下であり、下限としては５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上である。 The total content of nonionic water-soluble monomers is up to 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less based on 100% by mass of the photocurable composition for support material. The lower limit is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more.
また、上記サポート材用光硬化性組成物に含まれる単量体総量に対する、上記イオン性水溶性単量体の含有量と上記非イオン性水溶性単量体の含有量の合計である水溶性単量体の含有量は、上記サポート材用光硬化性組成物の水溶性を向上させる観点から、４５～１００質量％であることが好ましく、５０～１００質量％であることがより好ましい。 Furthermore, the water-soluble composition is the sum of the content of the ionic water-soluble monomer and the content of the non-ionic water-soluble monomer with respect to the total amount of monomers contained in the photocurable composition for support material. The content of the monomer is preferably 45 to 100% by mass, more preferably 50 to 100% by mass, from the viewpoint of improving the water solubility of the photocurable composition for support material.
（非イオン性非水溶性単量体）
上記サポート材用光硬化性組成物は、上記水溶性単量体以外の他の不飽和単量体（例えば、水溶解度（２０℃）が２０ｇ／Ｌ未満の非イオン性非水溶性単量体）を含んでいてもよい。上記非イオン性非水溶性単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ｎ－ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシエトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、メトキシエトキシエチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、２－エチルヘキシル－ジグリコール（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－シアノエチル（メタ）アクリレート、メチル＝２－（ヒドロキシメチル）アクリレート、および２－エチルヘキシルカルビトール（メタ）アクリレート等の（メタ）アクリレート；フェニルアリルエーテル、ｏ－，ｍ－，ｐ－クレゾールモノアリルエーテル、ビフェニル－２－オールモノアリルエーテル、ビフェニル－４－オールモノアリルエーテル、ブチルアリルエーテル、シクロヘキシルアリルエーテル、およびシクロヘキサンメタノールモノアリルエーテル等のアリルエーテル；ブチルビニルエーテル、ブチルプロペニルエーテル、ブチルブテニルエーテル、ヘキシルビニルエーテル、エチルヘキシルビニルエーテル、フェニルビニルエーテル、ベンジルビニルエーテル、エチルエトキシビニルエーテル、アセチルエトキシエトキシビニルエーテル、シクロヘキシルビニルエーテル、およびアダマンチルビニルエーテル等のビニルエーテル；フェニルマレイミド、シクロヘキシルマレイミド、およびｎ－ヘキシルマレイミド等のマレイミド；ベンジルアクリレート、フェノキシエチルアクリレート、フェノキシエトキシエチルアクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ビスフェノールＡジアクリレート、ビスフェノールＡのＥＯ付加物ビス（メタ）アクリレート、ビスフェノールＡのＰＯ付加物ビス（メタ）アクリレート、水添ビスフェノールＡのＥＯ付加物ビス（メタ）アクリレート等の芳香族基を有するモノマーおよび脂環式基を有するモノマー；ポリオキシエチレンジ（メタ）アクリレート、ポリオキシプロピレンジ（メタ）アクリレート等のポリオキシアルキレンジ（メタ）アクリレート；ヒドロキシアルキル（メタ）アクリレート等が挙げられる。
これらは１種で単独使用してもよく、２種以上を併用してもよい。
(Nonionic water-insoluble monomer)
The photocurable composition for a support material contains other unsaturated monomers other than the water-soluble monomer (for example, a nonionic water-insoluble monomer with a water solubility (20°C) of less than 20 g/L). ) may be included. Examples of the nonionic water-insoluble monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentyl (meth)acrylate, ) acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate , isomyristyl (meth)acrylate, isostearyl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, Methoxyethyl (meth)acrylate, Butoxyethyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Isobornyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentanyl (meth)acrylate, Methoxyethoxyethyl (meth)acrylate ) acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, t-butylcyclohexyl (meth) Acrylate, 2-ethylhexyl-diglycol (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, methyl 2-(hydroxymethyl)acrylate, and 2-ethylhexylcarbitol (meth)acrylate (meth)acrylates such as phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, and allyl ethers such as cyclohexane methanol monoallyl ether; butyl vinyl ether, butyl propenyl ether, butyl butenyl ether, hexyl vinyl ether, ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, ethyl ethoxy vinyl ether, acetyl ethoxy ethoxy vinyl ether, cyclohexyl vinyl ether, and adamantyl vinyl ether vinyl ethers such as phenylmaleimide, cyclohexylmaleimide, and n-hexylmaleimide; benzyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl ( Aromatic compounds such as meth)acrylate, bisphenol A diacrylate, bisphenol A EO adduct bis(meth)acrylate, bisphenol A PO adduct bis(meth)acrylate, hydrogenated bisphenol A EO adduct bis(meth)acrylate, etc. monomers having groups and monomers having alicyclic groups; polyoxyalkylene di(meth)acrylates such as polyoxyethylene di(meth)acrylate and polyoxypropylene di(meth)acrylate; hydroxyalkyl(meth)acrylates, etc. It will be done.
These may be used alone or in combination of two or more.
上記非イオン性非水溶性単量体の含有量としては、上記組成物１００質量％中、５０質量％以下であり、好ましくは２０～５０質量％、より好ましくは２５～４５質量％である。また、非イオン性非水溶性単量体の含有量が、サポート材用光硬化性組成物１００質量％中、５質量％未満であることも好ましく、０質量％であってもよい。このようにした場合に、サポート材用光硬化性組成物の臭気をより抑制できる。 The content of the nonionic water-insoluble monomer is 50% by mass or less, preferably 20 to 50% by mass, more preferably 25 to 45% by mass, based on 100% by mass of the composition. Further, the content of the nonionic water-insoluble monomer is preferably less than 5% by mass, and may be 0% by mass, based on 100% by mass of the photocurable composition for support material. In this case, the odor of the photocurable composition for support material can be further suppressed.
また、サポート材用光硬化性組成物の水溶性を向上させる観点から、上記非イオン性非水溶性単量体の含有量としては、０質量％以上５０質量％未満であることが好ましく、０質量％以上４０質量％未満であることがより好ましい。なお、２種以上含まれる場合、含有量は、各成分の含有量の合計である。 Further, from the viewpoint of improving the water solubility of the photocurable composition for support material, the content of the nonionic water-insoluble monomer is preferably 0% by mass or more and less than 50% by mass, and 0% by mass or more and less than 50% by mass. More preferably, it is at least 40% by mass and less than 40% by mass. In addition, when two or more types are included, the content is the total content of each component.
上記サポート材用光硬化性組成物には重合開始剤が含まれていることが好ましい。上記重合開始剤としては、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、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル等のベンゾイン化合物；アセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、２－ヒドロキシ－２－メチル－フェニルプロパン－１－オン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン等のアセトフェノン化合物；２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、２－クロロアントラキノン、２－アミルアントラキノン等のアントラキノン化合物；２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、［３－（３，４－ジメチル－９－オキソチオキサンテン－２－イル）オキシ－２－ヒドロキシプロピル］－トリメチルアザニウムクロリド等のチオキサントン化合物；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール化合物；ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、４，４’－ビスメチルアミノベンゾフェノン等のベンゾフェノン化合物；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、ビス－（２、６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキシド等のホスフィンオキシド；およびこれらの混合物等が挙げられる。
これらは１種で単独使用してもよく、２種以上を併用してもよい。
It is preferable that the photocurable composition for support material contains a polymerization initiator. Examples of the polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl ]-Acetophenone compounds such as 2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thioxanthone compounds such as isopropylthioxanthone, 2-chlorothioxanthone, [3-(3,4-dimethyl-9-oxothioxanthen-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; acetophenone dimethyl ketal, benzyl Ketal compounds such as dimethyl ketal; Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2 , 6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and mixtures thereof.
These may be used alone or in combination of two or more.
重合開始剤の含有量としては、例えば、上記水溶性単量体１００質量％に対して、好ましくは０．０５～１０．０質量％、より好ましくは０．１～７．０質量％、さらに好ましくは０．２～５．０質量％、特に好ましくは０．５～４．０質量％である。 The content of the polymerization initiator is, for example, preferably 0.05 to 10.0 mass%, more preferably 0.1 to 7.0 mass%, and more preferably 0.05 to 10.0 mass%, based on 100 mass% of the water-soluble monomer. It is preferably 0.2 to 5.0% by weight, particularly preferably 0.5 to 4.0% by weight.
上記サポート材用光硬化性組成物は、溶媒を含んでいてもよい。上記溶媒としては、プロピレングリコール、ジエチレングリコール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノプロピルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノメチルエーテルアセテート、グリセロール、ポリオキシエチレングリコール、ポリオキシプロピレングリコールなどのオキシプロピレン基を含むアルキレンオキサイド付加物等のグリコールが挙げられる。上記溶剤は１種のみを使用してもよく、２種以上を併用してもよい。
上記溶媒は、サポート材用光硬化性組成物１００質量％中、水の含有量が１．０質量％以下となるように使用する。上記溶媒としては、炭素数３～６のグリコールが好ましく、プロピレングリコール、ジエチレングリコール、グリセロールがより好ましく、プロピレングリコール、グリセロールが特に好ましい。
The photocurable composition for support material may contain a solvent. The above solvents include propylene glycol, diethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, glycerol, polyoxyethylene glycol, polyoxypropylene Examples include glycols such as alkylene oxide adducts containing oxypropylene groups such as glycols. The above solvents may be used alone or in combination of two or more.
The above-mentioned solvent is used so that the content of water is 1.0% by mass or less in 100% by mass of the photocurable composition for support material. The above-mentioned solvent is preferably a glycol having 3 to 6 carbon atoms, more preferably propylene glycol, diethylene glycol, or glycerol, and particularly preferably propylene glycol or glycerol.
上記組成物１００質量％中、上記溶媒の含有量は、下限としては、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは１５質量％以上、上限としては、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。但し、上記組成物１００質量％中、水の含有量は１．０質量％以下である。 The content of the solvent in 100% by mass of the composition has a lower limit of preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and an upper limit of preferably 80% by mass. % or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. However, the content of water is 1.0% by mass or less in 100% by mass of the above composition.
上記炭素数３～６のグリコールは合計で、上記組成物１００質量％中、３０～７０質量％含まれていることが好ましく、３５～６５質量％含まれていることがより好ましく、４０～６０質量％含まれていることがさらに好ましく、４５～５５質量％含まれていることが特に好ましい。
中でも、上記組成物１００質量％中、プロピレングリコールもしくはグリセロールの含有量が、３０～７０質量％であることが好ましく、３５～６５質量％であることがより好ましく、４０～６０質量％であることがさらに好ましく、４５～５５質量％であることが特に好ましい。
The total amount of the glycols having 3 to 6 carbon atoms is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and 40 to 60% by mass, based on 100% by mass of the composition. It is more preferable that the content is 45 to 55% by weight, particularly preferably 45 to 55% by weight.
Among these, the content of propylene glycol or glycerol in 100% by mass of the above composition is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and 40 to 60% by mass. is more preferable, and particularly preferably 45 to 55% by mass.
上記サポート材用光硬化性組成物には、必要によりその他の添加剤を含有させることができる。具体的には、例えば、光開始助剤、重合禁止剤、界面活性剤、着色剤、酸化防止剤、連鎖移動剤、充填剤等が挙げられる。 The photocurable composition for support material may contain other additives if necessary. Specific examples include photoinitiation aids, polymerization inhibitors, surfactants, colorants, antioxidants, chain transfer agents, fillers, and the like.
光開始助剤としては、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジエチルアニリン、Ｎ，Ｎ－ジメチル－ｐ－トルイジン、Ｎ，Ｎ－ジメチルアミノ－ｐ－安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ－ｐ－安息香酸イソアミルエチルエステル、Ｎ，Ｎ－ジヒドロキシエチルアニリン、トリエチルアミンおよびＮ，Ｎ－ジメチルヘキシルアミン等の第３級アミン化合物が挙げられる。 Photoinitiation aids include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethylamino-p-benzoic acid ethyl ester, N,N-dimethyl Examples include tertiary amine compounds such as amino-p-benzoic acid isoamylethyl ester, N,N-dihydroxyethylaniline, triethylamine and N,N-dimethylhexylamine.
重合禁止剤としては、（アルキル）フェノール、ハイドロキノン、カテコール、レゾルシン、ｐ－メトキシフェノール、ｔ－ブチルカテコール、ｔ－ブチルハイドロキノン、ピロガロール、１，１－ピクリルヒドラジル、フェノチアジン、ｐ－ベンゾキノン、ニトロソベンゼン、２，５－ジ－ｔ－ブチル－ｐ－ベンゾキノン、ジチオベンゾイルジスルフィド、ピクリン酸、クペロン、アルミニウムＮ－ニトロソフェニルヒドロキシルアミン、トリ－ｐ－ニトロフェニルメチル、Ｎ－（３－オキシアニリノ－１，３－ジメチルブチリデン）アニリンオキシド、ジブチルクレゾール、シクロヘキサノンオキシムクレゾール、グアヤコール、ｏ－イソプロピルフェノール、ブチラルドキシム、メチルエチルケトキシム、シクロヘキサノンオキシム等が挙げられる。 Polymerization inhibitors include (alkyl)phenol, hydroquinone, catechol, resorcinol, p-methoxyphenol, t-butylcatechol, t-butylhydroquinone, pyrogallol, 1,1-picrylhydrazyl, phenothiazine, p-benzoquinone, and nitrosinol. Benzene, 2,5-di-t-butyl-p-benzoquinone, dithiobenzoyl disulfide, picric acid, cuperone, aluminum N-nitrosophenylhydroxylamine, tri-p-nitrophenylmethyl, N-(3-oxyanilino-1, Examples include 3-dimethylbutylidene) aniline oxide, dibutyl cresol, cyclohexanone oximcresol, guaiacol, o-isopropylphenol, butyraldoxime, methyl ethyl ketoxime, and cyclohexanone oxime.
界面活性剤としては、ノニルフェノールのエチレンオキサイド（以下ＥＯと略記）１～４０モル付加物、ステアリン酸ＥＯ１～４０モル付加物等のＰＥＧ型非イオン界面活性剤；ソルビタンパルミチン酸モノエステル、ソルビタンステアリン酸モノエステル、ソルビタンステアリン酸トリエステル等の多価アルコール型非イオン界面活性剤；パーフルオロアルキルＥＯ１～５０モル付加物、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルベタイン等のフッ素含有界面活性剤；ポリエーテル変性シリコーンオイル、（メタ）アクリレート変性シリコーンオイル等の変性シリコーンオイル等が挙げられる。 Examples of surfactants include PEG-type nonionic surfactants such as ethylene oxide (hereinafter abbreviated as EO) 1 to 40 mol adduct of nonylphenol and 1 to 40 mol adduct of stearic acid; sorbitan palmitic acid monoester, sorbitan stearic acid. Polyhydric alcohol-type nonionic surfactants such as monoesters and sorbitan stearate triesters; fluorine-containing surfactants such as perfluoroalkyl EO 1 to 50 mole adducts, perfluoroalkyl carboxylates, perfluoroalkyl betaines; Examples include modified silicone oils such as ether-modified silicone oil and (meth)acrylate-modified silicone oil.
着色剤としては、トルイジンレッド、パーマネントカーミンＦＢ、ファストイエローＧ、ジスアゾイエローＡＡＡ、ジスアゾオレンジＰＭＰ、溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料、フタロシアニンブルー、インダントロンブルー、キナクリドンレッド、ジオキサジンバイオレット、塩基性染料、酸性染料、アニリンブラック、昼光蛍光顔料、ニトロソ顔料、ニトロ顔料、天然顔料、無機顔料としての金属酸化物、カーボンブラック等が挙げられる。 Colorants include toluidine red, permanent carmine FB, fast yellow G, disazo yellow AAA, disazo orange PMP, soluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, and base. Examples include natural pigments, acidic dyes, aniline black, daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, metal oxides as inorganic pigments, and carbon black.
酸化防止剤としては、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、ジラウリル３，３’－チオジプロピオネート、トリフェニルホスファイト、オクチル化ジフェニルアミン、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）等が挙げられる。 As antioxidants, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, dilauryl 3,3'-thiodipropionate, Examples include triphenyl phosphite, octylated diphenylamine, 2,6-di-t-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), and the like.
連鎖移動剤としては、ヒドロキノン、ジエチルメチルアミン、ジフェニルアミン、ジエチルジスルフィド、ジ－１－オクチルジスルフィド、トルエン、キシレン、１－ブテン、１－ノネン、ジクロロメタン、四塩化炭素、メタノール、１－ブタノール、エチルチオール、１－オクチルチオール、アセトン、メチルエチルケトン、２－メチル－２－プロピルアルデヒド、１－ペンチルアルデヒド、フェノール、ｍ－クレゾール、ｐ－クレゾール、ｏ－クレゾール等が挙げられる。 Chain transfer agents include hydroquinone, diethylmethylamine, diphenylamine, diethyl disulfide, di-1-octyl disulfide, toluene, xylene, 1-butene, 1-nonene, dichloromethane, carbon tetrachloride, methanol, 1-butanol, ethylthiol. , 1-octylthiol, acetone, methyl ethyl ketone, 2-methyl-2-propyl aldehyde, 1-pentyl aldehyde, phenol, m-cresol, p-cresol, o-cresol and the like.
充填剤としては、アルミナ粉、シリカ粉、タルク、マイカ、クレー、水酸化アルミニウム、炭酸カルシウム、ケイ酸カルシウム、アルミニウム粉、銅粉、炭素繊維、ガラス繊維、コットン繊維、ナイロン繊維、アクリル繊維、レーヨン繊維、マイクロバルーン、カーボンブラック、金属硫化物、木粉等が挙げられる。 Fillers include alumina powder, silica powder, talc, mica, clay, aluminum hydroxide, calcium carbonate, calcium silicate, aluminum powder, copper powder, carbon fiber, glass fiber, cotton fiber, nylon fiber, acrylic fiber, and rayon. Examples include fibers, microballoons, carbon black, metal sulfides, and wood flour.
上記サポート材用光硬化性組成物は必要に応じて、さらに、その他の添加剤を、本発明の効果を害しない範囲内において含んでいてもよい。例えば、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤、防錆剤、ｐＨ調整剤、表面張力調整剤、消泡剤、粘度調整剤、分散剤、分散安定剤、キレート剤、乾燥防止剤（湿潤剤）、着色剤、褪色防止剤、比抵抗調整剤、皮膜調整剤、酸化防止剤、及び界面活性剤等の公知の添加剤が挙げられる。これらの各種添加剤は、たとえば直接添加できる。 The photocurable composition for a support material may further contain other additives as necessary within a range that does not impair the effects of the present invention. For example, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, antifungal agents, rust inhibitors, pH adjusters, surface tension adjusters, antifoaming agents, viscosity adjusters, dispersants, dispersion stabilizers, chelates. Known additives include a drying agent (wetting agent), a colorant, a fading inhibitor, a resistivity regulator, a film regulator, an antioxidant, and a surfactant. These various additives can be added directly, for example.
上記添加物は、単独で用いてもよいし、２種以上を組み合わせて使用してもよい。
上記添加物の含有量としては、上記組成物１００質量％中、好ましくは０．０２～３０質量％、より好ましくは０．０５～２０質量％である。
The above additives may be used alone or in combination of two or more.
The content of the additive is preferably 0.02 to 30% by weight, more preferably 0.05 to 20% by weight based on 100% by weight of the composition.
上記サポート材用光硬化性組成物は、硬化後の硬化物がサポート材として使用されるため、サポート材の必須要件として、硬化物の硬度が優れている。硬度は、例えば、サポート材用光硬化性組成物を２ｃｍ×２ｃｍ×４ｍｍの穴が開いたシリコン枠に流し込み、メタルハライドランプで紫外線を５００ｍＪ／ｃｍ２照射して硬化させた場合に、Ｅデュロメーターにおける測定開始から１５秒後の硬度が５０以上であることが好ましく、６０以上であることがより好ましく、７０以上であることが特に好ましい。 In the photocurable composition for support material, since the cured product after curing is used as the support material, the hardness of the cured product is excellent as an essential requirement for the support material. For example, the hardness can be determined by pouring the photocurable composition for support material into a silicone frame with a hole of 2 cm x 2 cm x 4 mm, and curing it by irradiating it with ultraviolet rays of 500 mJ/ cm2 using a metal halide lamp. The hardness 15 seconds after the start of measurement is preferably 50 or more, more preferably 60 or more, and particularly preferably 70 or more.
上記サポート材用光硬化性組成物は、硬化後の硬化物がサポート材として使用されるため、サポート材の必須要件として、硬化物の水溶性が優れている。水溶性は、例えば、硬化物０．５ｇ（表面積４ｃｍ２）を金網の上に置き、常温（例えば２５℃前後）の水５ｇ中に浸漬した場合に、１２０分以内に溶解することが好ましく、９０分以内に溶解して不溶物が目視で観察されないことがより好ましい。 Since the photocurable composition for a support material is used as a support material after curing, the cured product has excellent water solubility, which is an essential requirement for the support material. Regarding water solubility, for example, when 0.5 g (surface area 4 cm 2 ) of the cured product is placed on a wire mesh and immersed in 5 g of water at room temperature (for example, around 25° C.), it is preferable that it dissolves within 120 minutes. More preferably, it dissolves within 90 minutes and no insoluble matter is visually observed.
上記サポート材用光硬化性組成物は、硬化後の硬化物がサポート材として使用されるため、サポート材の必須要件として、硬化物のブリードアウト性が優れている。ブリードアウト性は、例えば、サポート材用光硬化性組成物を２ｃｍ×２ｃｍ×４ｍｍの穴が開いたシリコン枠に流し込み、メタルハライドランプで紫外線を５００ｍＪ／ｃｍ２照射して硬化させた後に、硬化物を６０℃、５０％ＲＨに設定した恒温恒湿機中に５時間静置し、静置後のブリードアウトが目視にて認められないことが好ましい。 Since the photocurable composition for a support material is used as a support material after curing, the cured product has excellent bleed-out properties, which is an essential requirement for the support material. The bleed-out property can be determined, for example, by pouring a photocurable composition for a support material into a silicone frame with a hole of 2 cm x 2 cm x 4 mm, and curing it by irradiating it with ultraviolet rays at 500 mJ/ cm2 using a metal halide lamp. It is preferable that the sample be allowed to stand for 5 hours in a constant temperature and humidity machine set at 60° C. and 50% RH, and that no bleed-out is visually observed after being left still.
上記サポート材用光硬化性組成物は、上述した各種成分を用いて調製することができ、その調製手段や条件は特に限定されないが、例えば、一般的な撹拌羽根や超音波ホモジナイザー、高速ホモジナイザー、高圧ホモジナイザー、遊星撹拌装置、３本ロール、ボールミル、キティーミル、ディスクミル、ピンミル、ダイノーミル等の混合又は撹拌できる装置を用いて撹拌・混合する方法が挙げられる。溶液調製後に各種フィルターを用いてろ過をしてもよい。 The photocurable composition for support material can be prepared using the various components mentioned above, and the preparation means and conditions are not particularly limited, but examples include a general stirring blade, an ultrasonic homogenizer, a high-speed homogenizer, Examples include a method of stirring and mixing using a device that can mix or stir, such as a high-pressure homogenizer, a planetary stirrer, a three-roll mill, a ball mill, a kitty mill, a disk mill, a pin mill, and a dyno mill. After the solution is prepared, it may be filtered using various filters.
上記サポート材用光硬化性組成物は、ｐＨが５～８である。このため、３Ｄプリンターのプリンターヘッドの腐食を抑制できる。 The photocurable composition for support material has a pH of 5 to 8. Therefore, corrosion of the printer head of the 3D printer can be suppressed.
上記サポート材用光硬化性組成物では、２５℃における粘度は５～３００ｍＰａ・ｓが好ましい。また、２５℃における表面張力は２５～７０ｍＮ／ｍが好ましい。 The photocurable composition for a support material preferably has a viscosity of 5 to 300 mPa·s at 25°C. Further, the surface tension at 25° C. is preferably 25 to 70 mN/m.
上記サポート材用光硬化性組成物は、インクジェットヘッドからの吐出性を良好にする観点からは、吐出温度での粘度が２０ｍＰａ・ｓ以下であることが好ましい。なお、サポート材用光硬化性組成物の粘度測定は、ＪＩＳ Ｚ ８８０３に準拠し、Ｒ１００型粘度計を用いて行われる。 The photocurable composition for support material preferably has a viscosity of 20 mPa·s or less at the ejection temperature from the viewpoint of improving ejection properties from an inkjet head. The viscosity of the photocurable composition for support material is measured using an R100 viscometer in accordance with JIS Z 8803.
上記サポート材用光硬化性組成物は、インクジェット用３Ｄプリンター用サポート材用光硬化性組成物として使用することが好ましい。インクジェットヘッドからの吐出性を良好にする観点からは、吐出温度での表面張力が２５．０～３５．０ｍＮ／ｍであることが好ましい。表面張力の測定は、例えば、全自動平衡式エレクトロ表面張力計ＥＳＢ－Ｖ（共和界面科学社製）を用いて行われる。 The photocurable composition for a support material is preferably used as a photocurable composition for a support material for an inkjet 3D printer. From the viewpoint of improving the ejection properties from the inkjet head, the surface tension at the ejection temperature is preferably 25.0 to 35.0 mN/m. The surface tension is measured using, for example, a fully automatic balancing electro-surface tension meter ESB-V (manufactured by Kyowa Interface Science).
［３Ｄプリンター用サポート材］
本発明の３Ｄプリンター用サポート材は、濁度が４０％未満である。本発明の３Ｄプリンター用サポート材では、濁度が４０％未満であるため、透明性に優れており、該サポート材がモデル材に残留した場合でも、外観に優れた造形物を製造できる。また、本発明の３Ｄプリンター用サポート材は、硬化後の硬化物の全光線透過率が６０％以上であることが好ましく、７０％以上であることがより好ましい。上記全光線透過率と濁度は、ヘイズメーターを用いて測定できる。
[Support material for 3D printer]
The support material for a 3D printer of the present invention has a turbidity of less than 40%. Since the support material for a 3D printer of the present invention has a turbidity of less than 40%, it has excellent transparency, and even if the support material remains in the model material, a molded object with an excellent appearance can be manufactured. Further, in the support material for a 3D printer of the present invention, the total light transmittance of the cured product after curing is preferably 60% or more, more preferably 70% or more. The total light transmittance and turbidity can be measured using a haze meter.
本発明の３Ｄプリンター用サポート材は、上記本発明の３Ｄプリンター用サポート材用光硬化性組成物を硬化することにより、製造できる。上記本発明の３Ｄプリンター用サポート材用光硬化性組成物の硬化は、１００～２０００ｍＪ／ｃｍ２程度の紫外線を、上記本発明の３Ｄプリンター用サポート材用光硬化性組成物に照射して光硬化させることで実施できる。本発明の３Ｄプリンター用サポート材を、上記本発明の３Ｄプリンター用サポート材用光硬化性組成物を硬化させて得ることにより、透明性と水溶性に優れたサポート材を得ることができる。 The support material for a 3D printer of the present invention can be produced by curing the photocurable composition for a support material for a 3D printer of the present invention. The photocurable composition for a support material for a 3D printer of the present invention is cured by irradiating the photocurable composition for a support material for a 3D printer of the present invention with ultraviolet rays of about 100 to 2000 mJ/cm 2 . This can be done by curing. By obtaining the support material for a 3D printer of the present invention by curing the photocurable composition for a support material for a 3D printer of the present invention, a support material with excellent transparency and water solubility can be obtained.
［光造形品の製造方法］
光造形品の製造方法は、サポート材の形成工程と；モデル材の形成工程と；該サポート材の除去工程とを含んでいる。
[Manufacturing method for stereolithography]
The method for manufacturing a stereolithographic article includes a step of forming a support material; a step of forming a model material; and a step of removing the support material.
サポート材の形成工程では、上記本発明の３Ｄプリンター用サポート材用光硬化性組成物をノズルから噴射、印刷等にて造形後、１００～２０００ｍＪ／ｃｍ２程度の紫外線を照射して光硬化させて、上記本発明の３Ｄプリンター用サポート材を形成する。 In the step of forming a support material, the photocurable composition for a support material for a 3D printer of the present invention is sprayed from a nozzle, shaped by printing, etc., and then photocured by irradiation with ultraviolet rays of about 100 to 2000 mJ/ cm2. Thus, the support material for a 3D printer of the present invention is formed.
モデル材の形成工程では、公知のモデル材用組成物をノズルから噴射、印刷等にて造形後、１００～２０００ｍＪ／ｃｍ２程度の紫外線を照射して光硬化させてモデル材を形成する。 In the step of forming a model material, a known composition for model material is formed by spraying from a nozzle, printing, etc., and then irradiated with ultraviolet rays of about 100 to 2000 mJ/cm 2 to photocure to form a model material.
サポート材の除去工程では、本発明の３Ｄプリンター用サポート材用光硬化性組成物を硬化して得たサポート材が透明性と水溶性に優れているため、サポート材を水等の極性溶媒にて容易に除去でき、また、除去されずに残留していでも外観に優れた造形品を製造できる。
除去方法としては、安全面やコスト面から、硬化物を水中に静置してサポート材を除去する方法が好ましい。
In the support material removal step, since the support material obtained by curing the photocurable composition for support materials for 3D printers of the present invention has excellent transparency and water solubility, the support material is removed in a polar solvent such as water. It can be easily removed, and even if it remains without being removed, a molded article with an excellent appearance can be manufactured.
As the removal method, from the viewpoint of safety and cost, it is preferable to leave the cured product in water and remove the support material.
上記光造形物の製造方法では、上記本発明の３Ｄプリンター用サポート材用光硬化性組成物を硬化してなる上記本発明の３Ｄプリンター用サポート材が、透明性と水溶性に優れているため、外観に優れた光造形品を製造できる。 In the method for manufacturing a stereolithographic object, the support material for a 3D printer of the present invention obtained by curing the photocurable composition for a support material for a 3D printer of the present invention has excellent transparency and water solubility. , it is possible to manufacture stereolithographic products with excellent appearance.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the Examples below, and modifications may be made as appropriate within the scope of the spirit of the preceding and following. Of course, other implementations are also possible, and all of them are included within the technical scope of the present invention.
・サポート材用光硬化性組成物の調製
表１に示す各成分を、表１に示す分量（質量部）にて配合し、混合撹拌装置を用いて均一に混合して実施例１～１１と比較例１～４のサポート材用光硬化性組成物を調製し、次いで光硬化した。硬化条件は、サポート材組成物を２ｃｍ×２ｃｍ×４ｍｍの穴が開いたシリコン枠に流し込み、メタルハライドランプで紫外線を５００ｍＪ／ｃｍ２照射して硬化させた。
実施例１～１１のサポート材用光硬化性組成物では、水の含有量は１．０質量％以下、ｐＨは５～８であった。
得られたサポート材用光硬化性組成物の硬化後の硬化物の全光線透過率及び濁度、硬度、溶解性、耐ブリードアウト性を下記の方法で評価した。結果を表１～２に示す。
・Preparation of photocurable composition for support material Each component shown in Table 1 was blended in the amount (parts by mass) shown in Table 1, and mixed uniformly using a mixing agitator to produce Examples 1 to 11. Photocurable compositions for support materials of Comparative Examples 1 to 4 were prepared and then photocured. The curing conditions were as follows: The support material composition was poured into a silicone frame with a hole of 2 cm x 2 cm x 4 mm, and was cured by irradiating it with ultraviolet rays of 500 mJ/cm 2 using a metal halide lamp.
In the photocurable compositions for support materials of Examples 1 to 11, the water content was 1.0% by mass or less and the pH was 5 to 8.
The total light transmittance, turbidity, hardness, solubility, and bleed-out resistance of the cured product of the obtained photocurable composition for support material after curing were evaluated by the following methods. The results are shown in Tables 1 and 2.
（１）硬化後の硬化物の全光線透過率及び濁度の評価
硬化後の硬化物の全光線透過率及び濁度を日本電色工業社製ヘイズメーターＮＤＨ－７０００型を使用して測定した。評価基準は、次の通りである。結果を表１～２に示す。
［全光線透過率］
〇 ：７０％以上
△ ：６０％以上７０％未満
× ：６０％未満
［濁度］
〇 ：４０％未満
△ ：４０％以上７０％未満
× ：７０％以上
(1) Evaluation of the total light transmittance and turbidity of the cured product after curing The total light transmittance and turbidity of the cured product after curing were measured using a haze meter NDH-7000 model manufactured by Nippon Denshoku Industries. . The evaluation criteria are as follows. The results are shown in Tables 1 and 2.
[Total light transmittance]
〇: 70% or more △: 60% or more but less than 70% ×: less than 60% [Turbidity]
〇: Less than 40% △: 40% or more and less than 70% ×: 70% or more
（２）硬化後の硬度評価
硬化後の硬化物について、デュロメーターＥ型（高分子計器社製）を用いて、硬さを測定して評価した。評価基準は、次の通りである。結果を表１～２に示す。
◎ ：８０以上
○ ：６０以上８０未満
△ ：４０以上６０未満
× ：４０未満
(2) Evaluation of hardness after curing The hardness of the cured product after curing was measured and evaluated using a durometer type E (manufactured by Kobunshi Keiki Co., Ltd.). The evaluation criteria are as follows. The results are shown in Tables 1 and 2.
◎: 80 or more ○: 60 or more and less than 80 △: 40 or more and less than 60 ×: less than 40
（３）溶解性評価
硬化後の硬化物片（１×１×０．５ｃｍ）を金網の上に置き、水温２５℃の水１０ｍＬに水中で保持し、溶解性を目視にて不溶物の有無で評価した。評価基準は、次の通りである。結果を表１～２に示す。
◎：１．５時間以内に溶解。
○：２時間以内に溶解。
△：３時間以内に溶解。
×：３時間以内に溶解せず。
(3) Solubility evaluation A piece of cured material (1 x 1 x 0.5 cm) after curing was placed on a wire mesh and kept in 10 mL of water at a water temperature of 25°C, and the solubility was visually checked for the presence or absence of insoluble matter. It was evaluated by The evaluation criteria are as follows. The results are shown in Tables 1 and 2.
◎: Dissolved within 1.5 hours.
○: Dissolved within 2 hours.
△: Dissolved within 3 hours.
×: Not dissolved within 3 hours.
（４）ブリードアウト評価
硬化後の硬化物を６０℃、５０％ＲＨに設定した恒温恒湿機中に５時間静置し、静置後のブリードアウトの有無を目視で評価した。結果を表１～２に示す。
〇：ブリードアウトなし。
×：ブリードアウトあり。
(4) Bleed-out evaluation The cured product was left standing in a constant temperature and humidity chamber set at 60° C. and 50% RH for 5 hours, and the presence or absence of bleed-out after standing was visually evaluated. The results are shown in Tables 1 and 2.
○: No bleed out.
×: Bleed out.
表１～２における化合物名は、以下のとおりである。
ＡＡＫ：アクリル酸カリウム（日本触媒社製）
ＡＡＺｎ：アクリル酸亜鉛（日本触媒社製）
ＡＣＭＯ：アクリロイルモルホリン（東京化成社製）
ＮＶＰ：Ｎ－ビニルピロリドン（日本触媒社製）
ＡＭ－９０Ｇ：メトキシポリエチレングリコール＃４００アクリレート（新中村化学工業社製）
ＮＩＰＡＭ：イソプロピルアクリルアミド（東京化成工業社製）
ＨＥＡＡ：ヒドロキシエチルアクリルアミド（東京化成社製）
ＡＯＭＡ：アリルオキシメチルアクリル酸メチル（日本触媒社製）
ＩＢＯＡ：イソボルニルアクリレート（日本触媒社製）
ＤＧ：ジエチレングリコール（富士フイルム和光純薬社製）
ＰＧ：プロピレングリコール（富士フイルム和光純薬社製）
ＤＧＭＥ：ジプロピレングリコールモノプロピルエーテル（日本乳化剤社製）
Ｇｌｙ：グリセリン（富士フイルム和光純薬社製）
ＰＰＧ４００：ポリプロピレングリコール４００（富士フイルム和光純薬社製）
ＭＥＨＱ：４－メトキシフェノール（富士フイルム和光純薬社製）
ＮＰＡＬ：Ｎ－ニトロソＮ－フェニルヒドロキシルアミンアンモニウム（東京化成工業社製）
ＴＥＭＰＯ：２，２，６，６－テトラメチルピペリジン１-オキシル（東京化成工業社製）
ＩｒｇＴＰＯ：２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド（ＢＡＳＦ社製）
Ｉｒｇ１８４：１－ヒドロキシシクロヘキシル―フェニルケトン（ＢＡＳＦ社製）
Ｉｒｇ２９５９：１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－メチルプロパノン（ＢＡＳＦ社製）
The compound names in Tables 1 and 2 are as follows.
AAK: Potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.)
AAZn: Zinc acrylate (manufactured by Nippon Shokubai Co., Ltd.)
ACMO: Acryloylmorpholine (manufactured by Tokyo Kasei Co., Ltd.)
NVP: N-vinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.)
AM-90G: Methoxypolyethylene glycol #400 acrylate (manufactured by Shin Nakamura Chemical Co., Ltd.)
NIPAM: Isopropylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
HEAA: Hydroxyethyl acrylamide (manufactured by Tokyo Kasei Co., Ltd.)
AOMA: Methyl allyloxymethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
IBOA: Isobornyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
DG: Diethylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
PG: Propylene glycol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DGME: Dipropylene glycol monopropyl ether (manufactured by Nippon Nyukazai Co., Ltd.)
Gly: Glycerin (manufactured by Fujifilm Wako Pure Chemical Industries)
PPG400: Polypropylene glycol 400 (manufactured by Fujifilm Wako Pure Chemical Industries)
MEHQ: 4-methoxyphenol (manufactured by Fujifilm Wako Pure Chemical Industries)
NPAL: N-nitroso N-phenylhydroxylamine ammonium (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
TEMPO: 2,2,6,6-tetramethylpiperidine 1-oxyl (manufactured by Tokyo Chemical Industry Co., Ltd.)
IrgTPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF)
Irg184: 1-hydroxycyclohexyl-phenyl ketone (manufactured by BASF)
Irg2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone (manufactured by BASF)
実施例のサポート材用光硬化性組成物では、イオン性水溶性単量体の含有量を１０質量％～８０質量％、非イオン性水溶性単量体の含有量を５質量％～５０質量％、非イオン性非水溶性単量体を０質量％～５０質量％、水の含有量を１．０質量％以下、ｐＨを５～８とすることにより、硬化後に、溶解性に優れ、且つ透明なサポート材が得られた。
In the photocurable composition for support material of the example, the content of ionic water-soluble monomers is 10% by mass to 80% by mass, and the content of nonionic water-soluble monomers is 5% by mass to 50% by mass. %, the nonionic water-insoluble monomer is 0% to 50% by mass, the water content is 1.0% by mass or less, and the pH is 5 to 8, so that it has excellent solubility after curing. Moreover, a transparent support material was obtained.
Claims (2)
非イオン性水溶性単量体（但し、アクリル酸を除く）を５質量％～５０質量％含み、
非イオン性非水溶性単量体を０質量％～５０質量％含み、
水の含有量が１．０質量％以下であり、
ｐＨが５～８である、
３Ｄプリンター用サポート材用光硬化性組成物。 10 % by mass or more of an ionic water-soluble monomer containing a water-soluble ethylenically unsaturated monomer containing a monovalent counter ion and a water-soluble ethylenically unsaturated monomer containing a polyvalent metal ion. Contains 80% by mass,
Contains 5% to 50% by mass of nonionic water-soluble monomers (excluding acrylic acid) ,
Contains 0% to 50% by mass of a nonionic water-insoluble monomer,
The water content is 1.0% by mass or less,
pH is 5 to 8,
Photocurable composition for support material for 3D printers.
A 3D printer support material obtained by curing the photocurable composition for a 3D printer support material according to claim 1, and having a turbidity of less than 40%.
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