JPWO2019195763A5 - - Google Patents
Download PDFInfo
- Publication number
- JPWO2019195763A5 JPWO2019195763A5 JP2020554897A JP2020554897A JPWO2019195763A5 JP WO2019195763 A5 JPWO2019195763 A5 JP WO2019195763A5 JP 2020554897 A JP2020554897 A JP 2020554897A JP 2020554897 A JP2020554897 A JP 2020554897A JP WO2019195763 A5 JPWO2019195763 A5 JP WO2019195763A5
- Authority
- JP
- Japan
- Prior art keywords
- light
- reflecting material
- photopolymerizable
- monomer
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 claims description 148
- 239000000463 material Substances 0.000 claims description 94
- 239000000178 monomer Substances 0.000 claims description 49
- 239000003211 photoinitiator Substances 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 14
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- 238000009472 formulation Methods 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 8
- YFHICDDUDORKJB-UHFFFAOYSA-N Trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 claims description 4
- AOLNDUQWRUPYGE-UHFFFAOYSA-N 1,4-dioxepan-5-one Chemical compound O=C1CCOCCO1 AOLNDUQWRUPYGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N dilactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002596 lactones Chemical group 0.000 claims description 4
- JMRZMIFDYMSZCB-UHFFFAOYSA-N morpholine-2,5-dione Chemical compound O=C1COC(=O)CN1 JMRZMIFDYMSZCB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- QORWJWZARLRLPR-UHFFFAOYSA-H Tricalcium phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 7
- 235000019731 tricalcium phosphate Nutrition 0.000 description 5
- 229920000591 gum Polymers 0.000 description 4
- 230000003000 nontoxic Effects 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- 229920002683 Glycosaminoglycan Polymers 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N Lauric acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920001721 Polyimide Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920001470 Polyketone Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004676 glycans Polymers 0.000 description 2
- 229920002674 hyaluronan Polymers 0.000 description 2
- 229960003160 hyaluronic acid Drugs 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 230000004962 physiological condition Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- MAKUBRYLFHZREJ-JWBQXVCJSA-M sodium;(2S,3S,4R,5R,6R)-3-[(2S,3R,5S,6R)-3-acetamido-5-hydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-4,5,6-trihydroxyoxane-2-carboxylate Chemical compound [Na+].CC(=O)N[C@@H]1C[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@H](O)[C@H]1O MAKUBRYLFHZREJ-JWBQXVCJSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BKESYGFNPLIPQF-GXRNKMMISA-N (2R,3S,4R,5R,6R)-5-amino-6-[[(2R,3S,4R,5R,6S)-5-amino-6-[(2S,3R,4R,5S,6R)-3-amino-4-[(2S,3R,4R,5S,6R)-3-amino-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-3,4-bis[[(2S,3R,4R,5S,6R)-3-amino-4,5-dihydroxy-6-(hydroxym Chemical compound N[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)[C@@H](N)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O3)N)[C@H](O)[C@@H](CO)O2)N)O1 BKESYGFNPLIPQF-GXRNKMMISA-N 0.000 description 1
- HYRUXGRHTJRKNG-SMBWEDIMSA-N (2S,3R,4R,5R,6R)-2-[(2R,3R,4R,5R,6S)-6-[(2R,3R,4R,5R,6R)-4,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)-5-methoxyoxane-3,4-diol Chemical compound O[C@@H]1[C@@H](O)[C@H](OC)O[C@H](CO)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H](O[C@H]2[C@@H]([C@@H](O)[C@@H](OC)[C@@H](CO)O2)O)[C@@H](CO)O1 HYRUXGRHTJRKNG-SMBWEDIMSA-N 0.000 description 1
- XUNYETCZGJEBDM-UHFFFAOYSA-N 1-phenyl-N-(2,2,6,6-tetramethyl-1-oxopiperidin-1-ium-4-yl)methanimine Chemical compound C1C(C)(C)[N+](=O)C(C)(C)CC1N=CC1=CC=CC=C1 XUNYETCZGJEBDM-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229940023476 Agar Drugs 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- XJKJWTWGDGIQRH-BFIDDRIFSA-N Alginic acid Chemical compound O1[C@@H](C(O)=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](C)[C@@H](O)[C@H]1O XJKJWTWGDGIQRH-BFIDDRIFSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229940092690 Barium Sulfate Drugs 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J Calcium pyrophosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- DJHJJVWPFGHIPH-OODMECLYSA-N Chitin Chemical compound O[C@@H]1C(NC(=O)C)[C@H](O)OC(CO)[C@H]1COC[C@H]1C(NC(C)=O)[C@@H](O)[C@H](COC[C@H]2C([C@@H](O)[C@H](O)C(CO)O2)NC(C)=O)C(CO)O1 DJHJJVWPFGHIPH-OODMECLYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- KXKPYJOVDUMHGS-OSRGNVMNSA-N Chondroitin sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](OS(O)(=O)=O)[C@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](C(O)=O)O1 KXKPYJOVDUMHGS-OSRGNVMNSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- 239000004134 Dicalcium diphosphate Substances 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K Dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 229920000855 Fucoidan Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229940014259 Gelatin Drugs 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- 229960002897 Heparin Drugs 0.000 description 1
- ZFGMDIBRIDKWMY-PASTXAENSA-N Heparin Chemical compound CC(O)=N[C@@H]1[C@@H](O)[C@H](O)[C@@H](COS(O)(=O)=O)O[C@@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O[C@H]2[C@@H]([C@@H](OS(O)(=O)=O)[C@@H](O[C@@H]3[C@@H](OC(O)[C@H](OS(O)(=O)=O)[C@H]3O)C(O)=O)O[C@@H]2O)CS(O)(=O)=O)[C@H](O)[C@H]1O ZFGMDIBRIDKWMY-PASTXAENSA-N 0.000 description 1
- 229940039371 Karaya Gum Drugs 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- QAQJMLQRFWZOBN-LAUBAEHRSA-N L-ascorbyl-6-palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O QAQJMLQRFWZOBN-LAUBAEHRSA-N 0.000 description 1
- 239000011786 L-ascorbyl-6-palmitate Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920000903 Polyhydroxyalkanoate Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N Trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 229940093612 Zein Drugs 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- 108010055615 Zein Proteins 0.000 description 1
- 229960001296 Zinc Oxide Drugs 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 235000010385 ascorbyl palmitate Nutrition 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910000394 calcium triphosphate Inorganic materials 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 229960005188 collagen Drugs 0.000 description 1
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- UWLPCYBIJSLGQO-UHFFFAOYSA-N dodecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCC(O)=O UWLPCYBIJSLGQO-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 229920000669 heparin Polymers 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 235000010485 konjac Nutrition 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- DJMVHSOAUQHPSN-KZSASMRXSA-N maltohexaose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O[C@H]([C@H](O)CO)[C@H](O)[C@@H](O)C=O)O[C@H](CO)[C@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O[C@@H]2[C@@H]([C@@H](O)[C@H](O[C@@H]3[C@@H]([C@@H](O)[C@H](O[C@@H]4[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O4)O)[C@@H](CO)O3)O)[C@@H](CO)O2)O)[C@@H](CO)O1 DJMVHSOAUQHPSN-KZSASMRXSA-N 0.000 description 1
- RXVWSYJTUUKTEA-CGQAXDJHSA-N maltotriose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O[C@H]([C@H](O)CO)[C@H](O)[C@@H](O)C=O)O[C@H](CO)[C@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 RXVWSYJTUUKTEA-CGQAXDJHSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- RFWLACFDYFIVMC-UHFFFAOYSA-D pentacalcium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O RFWLACFDYFIVMC-UHFFFAOYSA-D 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010491 tara gum Nutrition 0.000 description 1
- 239000000213 tara gum Substances 0.000 description 1
- FDFYYWMHPJTGEO-UHFFFAOYSA-K tetracalcium;phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O FDFYYWMHPJTGEO-UHFFFAOYSA-K 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
調合物番号５／ＰＥＧ－ＤＡ５７５に反射材料としてβ－リン酸三カルシウム（ＴＣＰ）を混合したブレンドの光硬化
５０／５０（ｗ／ｗ）の比率で実施例１及び２のメタクリレート化調合物番号５（トリメチレンカーボネート、カプロラクトン、及びグリコリドモノマーを含むＭn＝２３００ダルトンの特注ジメタクリレート線状ポリマー）とＰＥＧ－ＤＡ５７５（Ｓｉｇｍａ Ａｌｄｒｉｃｈ）、並びに光開始剤として０．２５％（ｗ／ｗ）のＢＡＰＯ、更に２５％（ｗ／ｗ）のＴＣＰを含む又は含まない光硬化性調合物のブレンドを調製した。両方の調合物を、ＵＶ光（Ｄｙｍａｘ Ｂｌｕｅ Ｗａｖｅ２００ ＵＶ光硬化スポットランプシステム）に３０ｍＷ／ｃｍ2の強度で０．２、０．５、及び１秒間暴露した。ＴＣＰを含まない調合物は０．５秒まで部分的な硬化が始まらず、１秒で表面硬化皮膜が形成された。これに対し、２５％のＴＣＰを含有する調合物は０．２秒で表面が硬化し、１秒でほぼ完全に硬化し、ＴＣＰの添加により硬化速度が速まったことが示された。
本発明の好ましい態様は、下記の通りである。
〔１〕物品を光重合印刷する方法であって、
ａ）光重合性組成物を一時的に光に暴露する工程であって、前記光重合性組成物が、
ｉ．少なくとも１種の光重合性マクロマー成分；
ｉｉ．前記光重合性組成物中に懸濁した少なくとも１種の光反射材料成分；及び
ｉｉｉ．少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、工程、並びに
ｂ）少なくとも重合マクロマーを含む印刷物を形成する工程
を含む、方法。
〔２〕前記光反射材料成分が、光が接する光重合性組成物の表面で、前記光反射材料成分を含まない同じ光重合性組成物と比べて重合速度を高める、前記〔１〕に記載の方法。
〔３〕光反射材料成分を光重合性組成物に組み込むことで、前記光反射材料成分を含まない光重合性組成物で使用する濃度よりも低い光開始剤濃度で前記マクロマーを表面硬化させる、前記〔１〕に記載の方法。
〔４〕前記光開始剤成分の総濃度が、１．０質量％未満である、前記〔１〕～〔３〕のいずれか一項に記載の方法。
〔５〕前記光重合性組成物が、反応性希釈剤を更に含む、前記〔１〕～〔４〕のいずれか一項に記載の方法。
〔６〕前記光重合性組成物が、非反応性希釈剤を更に含む、前記〔１〕～〔５〕のいずれか一項に記載の方法。
〔７〕前記光重合性組成物が、安定剤を更に含む、前記〔１〕～〔６〕のいずれか一項に記載の方法。
〔８〕前記安定剤が、フリーラジカル安定剤である、前記〔７〕に記載の方法。
〔９〕前記光反射材料成分が、粒子状光反射材料を含む、前記〔１〕～〔８〕のいずれか一項に記載の方法。
〔１０〕前記光重合性組成物が、活性剤を更に含む、前記〔１〕～〔９〕のいずれか一項に記載の方法。
〔１１〕前記印刷物を硬化させる工程を含む二次硬化工程を更に含む、前記〔１〕～〔１０〕のいずれか一項に記載の方法。
〔１２〕前記印刷物をすすぐ工程を更に含む、前記〔１〕～〔１１〕のいずれか一項に記載の方法。
〔１３〕前記光重合性組成物が、染料を更に含む、前記〔１〕～〔１２〕のいずれか一項に記載の方法。
〔１４〕前記光重合性マクロマー成分が、エチレン性不飽和基を有するモノマー、又はエチレン性不飽和基を有するモノマー単位（モノマー）を有するマクロマーを含む、前記〔１〕～〔１３〕のいずれか一項に記載の方法。
〔１５〕前記光重合性マクロマー成分が、チオール基を有するモノマー、又はチオール基を有するモノマー単位（モノマー）を有するマクロマーを含む、前記〔１〕～〔１３〕のいずれか一項に記載の方法。
〔１６〕前記光重合性マクロマー成分が、エチレン性不飽和基を有するモノマー、又はエチレン性不飽和基を有するモノマー単位（モノマー）を有するマクロマー、並びにチオール基を有するモノマー、又はチオール基を有するモノマー単位（モノマー）を有するマクロマーを含む、前記〔１〕～〔１３〕のいずれか一項に記載の方法。
〔１７〕前記光重合性マクロマー成分が、ラクトンモノマー、グリコリド、ラクチド、ε－カプロラクトン、トリメチレンカーボネート、ｐ－ジオキサノン、１，５－ジオキセパン－２－オン、若しくはモルホリン－２，５－ジオン、又はこれらの組み合わせのうちの少なくとも１種のモノマー単位を含むマクロマーを含む、前記〔１〕～〔１６〕のいずれか一項に記載の方法。
〔１８〕光重合に用いる光波長が、１０～７００ｎｍ（ＵＶ光１０～４００）（可視光３９０～７００）である、前記〔１〕～〔１７〕のいずれか一項に記載の方法。
〔１９〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも短い時間で光重合する、前記〔１〕～〔１８〕のいずれか一項に記載の方法。
〔２０〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも、同じ露光量（ｍＷ／ｃｍ
2
）で速い速度で光重合する、前記〔１〕～〔１９〕のいずれか一項に記載の方法。
〔２１〕前記光開始剤成分の濃度範囲が、約０．０１～約５．０質量％である、前記〔１〕～〔２０〕のいずれか一項に記載の方法。
〔２２〕少なくとも１種の光開始剤が、少なくとも１つの光反射材料によって反射される波長で吸収する、前記〔１〕に記載の方法。
〔２３〕硬化深さが、１５０ミクロン未満である、前記〔１〕に記載の方法。
〔２４〕前記光反射材料成分が、前記光重合性組成物の約５～約９０質量％を構成する、前記〔１〕に記載の方法。
〔２５〕前記光反射材料成分が、５００ミクロン未満の大きさの粒子状光反射材料を含む、前記〔１〕に記載の方法。
〔２６〕前記光反射材料成分が、有機化合物、無機化合物、又はこれらの組み合わせを含む光反射材料を含む、前記〔１〕に記載の方法。
〔２７〕前記光反射材料成分が、液体である光反射材料を含む、前記〔１〕に記載の方法。
〔２８〕前記光反射材料成分が、ポリマーである光反射材料を含む、前記〔１〕に記載の方法。
〔２９〕前記光反射材料成分が、生理的条件で吸収性である又は吸収性でない光反射材料を含む、前記〔１〕に記載の方法。
〔３０〕前記〔１〕～〔２９〕のいずれか一項に記載の方法によって重合されたポリマー。
〔３１〕前記〔１〕～〔３０〕のいずれか一項に記載の方法によって生産された物品。
〔３２〕医療機器である、前記〔３１〕に記載の物品。
〔３３〕光重合生分解性ポリマー及び非毒性量の光開始剤を含む、非毒性ポリマー物品。
〔３４〕光重合マクロマー及び非毒性量の光開始剤を含む、非毒性ポリマー組成物。
〔３５〕光重合光反射材料を更に含む、前記〔３４〕に記載の組成物。
〔３６〕光重合性組成物であって
ｉ）少なくとも１種の光重合性マクロマー成分；
ｉｉ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；及び
ｉｉｉ）少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない光重合性組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、光重合性組成物。
〔３７〕前記光反射材料成分が、光が接する光重合性組成物の表面で、前記光反射材料成分を含まない同じ光重合性組成物と比べて重合速度を高める、前記〔３６〕に記載の組成物。
〔３８〕光反射材料成分を光重合性組成物に組み込むことで、前記光反射材料成分を含まない光重合性組成物で使用する濃度よりも低い光開始剤濃度で前記マクロマーを表面硬化させる、前記〔３６〕に記載の組成物。
〔３９〕前記光開始剤濃度の総濃度が、１．０質量％未満である、前記〔３６〕に記載の組成物。
〔４０〕前記光重合性組成物が、反応性若しくは非反応性希釈剤、又は両方を更に含む、前記〔３６〕に記載の組成物。
〔４１〕前記光重合性組成物が、安定剤を更に含む、前記〔３６〕～〔４０〕のいずれか一項に記載の組成物。
〔４２〕前記光反射材料成分が、粒子状光反射材料を含む、前記〔３６〕に記載の組成物。
〔４３〕前記光重合性組成物が、活性剤を更に含む、前記〔３６〕に記載の組成物。
〔４４〕前記光反射材料成分が、活性剤を含む、前記〔４３〕に記載の組成物。
〔４５〕前記光反射材料が、活性剤である、前記〔４３〕に記載の組成物。
〔４６〕前記光反射材料が、活性剤を含む、前記〔４３〕に記載の組成物。
〔４７〕前記光重合性マクロマー成分が、活性剤を含む、前記〔４３〕に記載の組成物。
〔４８〕前記光重合性マクロマーが、活性剤を含む、前記〔４３〕に記載の組成物。
〔４９〕反応性希釈剤が、前記活性剤を含む、前記〔４３〕に記載の組成物。
〔５０〕非反応性希釈剤が、前記活性剤を含む、前記〔４３〕に記載の組成物。
〔５１〕前記光重合性組成物が、染料を更に含む、前記〔３６〕～〔５０〕のいずれか一項に記載の組成物。
〔５２〕前記光重合性マクロマー成分が、エチレン性不飽和基を有するモノマー、若しくはエチレン性不飽和基を有するモノマー単位（モノマー）を有するマクロマー、又はチオール基を有するモノマー、若しくはチオール基を有するモノマー単位（モノマー）を有するマクロマー、又はエチレン性不飽和基を有するモノマー、若しくはエチレン性不飽和基を有するモノマー単位（モノマー）を有するマクロマーと、チオール基を有するモノマー、若しくはチオール基を有するモノマー単位（モノマー）を有するマクロマーとの組み合わせを含む、前記〔３６〕～〔５１〕のいずれか一項に記載の組成物。
〔５３〕前記光重合性マクロマー成分が、ラクトンモノマー、グリコリド、ラクチド、ε－カプロラクトン、トリメチレンカーボネート、ｐ－ジオキサノン、１，５－ジオキセパン－２－オン、若しくはモルホリン－２，５－ジオン、又はこれらの組み合わせのうちの少なくとも１種のモノマー単位を含むマクロマーを含む、前記〔３６〕～〔５２〕のいずれか一項に記載の組成物。
〔５４〕前記光重合性組成物が、１０～７００ｎｍ（ＵＶ光１０～４００）（可視光３９０～７００）の光波長に暴露されると重合する、前記〔３６〕～〔５３〕のいずれか一項に記載の組成物。
〔５５〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも短い時間で光重合する、前記〔３６〕～〔５４〕のいずれか一項に記載の組成物。
〔５６〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも短い時間で光重合する、前記〔３６〕～〔５５〕のいずれか一項に記載の組成物。
〔５７〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも、同じ露光量（ｍＷ／ｃｍ
2
）で速い速度で光重合する、前記〔３６〕～〔５６〕のいずれか一項に記載の組成物。
〔５８〕前記光重合性組成物が、同じ重合条件下で前記反射材料を含まない光重合性組成物よりも、同じ露光量（ｍＷ／ｃｍ
2
）で速い速度で光重合する、前記〔３６〕～〔５７〕のいずれか一項に記載の組成物。
〔５９〕前記光開始剤が、前記光反射材料によって反射される波長で吸収する、前記〔３６〕～〔５８〕のいずれか一項に記載の組成物。
〔６０〕前記光反射材料成分が、前記光重合性組成物の約５～約６５質量％を構成する、前記〔３６〕～〔５９〕のいずれか一項に記載の組成物。
〔６１〕前記光反射材料成分が、生理的条件で吸収性である又は吸収性でない光反射材料を含む、前記〔３６〕～〔６０〕のいずれか一項に記載の組成物。
〔６２〕前記光反射材料成分が、光重合性マクロマー、希釈剤、光反射材料、又はこれらの組み合わせのうちの少なくとも１つと重合する光反射材料を含む、前記〔３６〕～〔６１〕のいずれか一項に記載の組成物。
〔６３〕光造形光重合性組成物であって、
ｉ）少なくとも１種の光重合性マクロマー成分；
ｉｉ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；及び
ｉｉｉ）少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記組成物の照射量要件を調整する、光造形光重合性組成物。
〔６４〕連続液界面製造の光重合性組成物であって、
ｉ）少なくとも１種の光重合性マクロマー成分；
ｉｉ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；及び
ｉｉｉ）少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記組成物の照射量要件を調整する、連続液界面製造の光重合性組成物。
〔６５〕ＤＬＰ（デジタルライトプロセシング）光重合性組成物であって、
ｉ）少なくとも１種の光重合性マクロマー成分；
ｉｉ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；及び
ｉｉｉ）少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記組成物の照射量要件を調整する、ＤＬＰ光重合性組成物。
〔６６〕光重合性インク組成物であって、
ａ）少なくとも１種の光重合性マクロマー成分；
ｂ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；
ｃ）少なくとも１種の光開始剤成分；
ｄ）反応性希釈剤；及び
ｅ）安定剤
を含み、前記光反射材料成分が、前記光反射材料を含まない光重合性組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、光重合性インク組成物。
〔６７〕光重合性インク組成物であって、
ａ）少なくとも１種の光重合性マクロマー成分；
ｂ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；
ｃ）少なくとも１種の光開始剤成分；
ｄ）反応性希釈剤；及び
ｅ）安定剤
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、光重合性インク組成物。
〔６８〕光反射材料であって、光重合性インク調合物に添加した場合に、前記光反射材料を含まないインク調合物の照射量要件と比較して、前記インク調合物の照射量要件を調整するように、無機固体、有機化合物、結晶性有機化合物、結晶性アミノ酸及び／若しくはその誘導体、結晶性脂肪酸及び／若しくはその誘導体、結晶性ペプチド、又はこれらの組み合わせのうちの少なくとも１つを含む、光反射材料。
〔６９〕前記無機化合物が、二酸化チタン、酸化亜鉛、硫酸バリウム、リン酸三カルシウム、リン酸二カルシウム、リン酸一カルシウム、ニリン酸二カルシウム、三リン酸カルシウム、ヒドロキシアパタイト、アパタイト、及びリン酸テトラカルシウム、又はこれらの組み合わせである、前記〔６８〕に記載の材料。
〔７０〕前記有機化合物が、ポリエステル、ポリウレタン、ポリエーテル、ポリ無水物、ポリアミド、ポリカーボネート、ポリケトン、ポリエチレン、ポリプロピレン、ポリビニルアルコール、ポリテトラフルオロエチレン、ポリ塩化ビニル、ポリイミド、及びポリヒドロキシアルカノエート、又はこれらの組み合わせの脂肪族ポリマー及びコポリマーを含む、前記〔６８〕に記載の材料。
〔７１〕前記有機化合物が、ポリエステル、ポリウレタン、ポリエーテル、ポリ無水物、ポリケトン、ポリアミド、ポリカーボネート、及びポリイミド、又はこれらの組み合わせの芳香族ポリマー及びコポリマーを含む、前記〔６８〕に記載の材料。
〔７２〕前記有機化合物が、シクロデキストリン、デンプン、ヒアルロン酸、脱アセチル化ヒアルロン酸、キトサン、トレハロース、セロビオース、マルトトリオース、マルトヘキサオース、キトヘキサオース、アガロース、キチン５０、アミロース、グルカン、ヘパリン、キシラン、ペクチン、ガラクタン、グリコサミノグリカン、デキストラン、アミノ化デキストラン、セルロース、ヒドロキシアルキルセルロース、カルボキシアルキルセルロース、フコイダン、コンドロイチン硫酸、硫酸多糖類、ムコ多糖類、ゼラチン、ゼイン、コラーゲン、アルギン酸、寒天、カラギーナン、グアーガム、アラビアガム、ガティガム、カラヤガム、コンニャクガム、タマリンドガム、タラガム、トラガカントガム、ローカストビーンガム、ペクチン、キサンタンガム、又はこれらの組み合わせの天然由来ポリマー及び誘導体を含む、前記〔６８〕に記載の材料。
〔７３〕前記結晶性有機化合物が、結晶性脂肪族及び芳香族ポリマー、並びにこれらの組み合わせを含む、前記〔６８〕に記載の材料。
〔７４〕前記結晶性有機化合物が、結晶性天然由来ポリマー及び誘導体、並びにこれらの組み合わせを含む、前記〔６８〕に記載の材料。
〔７５〕結晶性アミノ酸及びこれらの誘導体、並びにこれらの組み合わせを含む、前記〔６８〕に記載の材料。
〔７６〕前記結晶性脂肪酸が、パルミチン酸、パルミチン酸アスコルビル、ラウリン酸、モノラウリン酸グリセロール、ミリスチン酸、カプリン酸、及びこれらの組み合わせを含む、前記〔６８〕に記載の材料。
Polymerization Formulation Nos. of Examples 1 and 2 at a photocuring ratio of 50/50 (w / w) of a blend of Formulation No. 5 / PEG-DA575 mixed with β-tricalcium phosphate (TCP) as a reflective material. 5 ( Mn = 2300 Dalton custom dimethacrylate linear polymer containing trimethylene carbonate, caprolactone, and glycolide monomer) and PEG-DA575 (Sigma Aldrich), as well as 0.25% (w / w) as a photoinitiator. A blend of photocurable formulations with or without BAPO and 25% (w / w) TCP was prepared. Both formulations were exposed to UV light (Dymax Blue Wave200 UV photocurable spot lamp system) at an intensity of 30 mW / cm 2 for 0.2, 0.5, and 1 second. The TCP-free formulation did not start partial curing until 0.5 seconds, and a surface-hardened film was formed in 1 second. On the other hand, it was shown that the surface of the formulation containing 25% TCP was cured in 0.2 seconds and almost completely cured in 1 second, and the curing rate was increased by the addition of TCP.
Preferred embodiments of the present invention are as follows.
[1] A method of photopolymerizing printing of an article.
a) A step of temporarily exposing the photopolymerizable composition to light, wherein the photopolymerizable composition is:
i. At least one photopolymerizable macromer component;
ii. At least one light-reflecting material component suspended in the photopolymerizable composition; and
iii. At least one photoinitiator component
To adjust the dose requirement of the photopolymerizable composition when the light-reflecting material component comprises, and the light-reflecting material-free composition is compared to the dose requirement.
b) Step of forming a printed matter containing at least a polymerized macromer
Including, how.
[2] The above-mentioned [1], wherein the light-reflecting material component increases the polymerization rate on the surface of the photopolymerizable composition in contact with light as compared with the same photopolymerizable composition containing no light-reflecting material component. the method of.
[3] By incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a photoinitiator concentration lower than the concentration used in the photopolymerizable composition containing no light-reflecting material component. The method according to the above [1].
[4] The method according to any one of [1] to [3] above, wherein the total concentration of the photoinitiator component is less than 1.0% by mass.
[5] The method according to any one of [1] to [4] above, wherein the photopolymerizable composition further contains a reactive diluent.
[6] The method according to any one of [1] to [5] above, wherein the photopolymerizable composition further contains a non-reactive diluent.
[7] The method according to any one of [1] to [6] above, wherein the photopolymerizable composition further contains a stabilizer.
[8] The method according to [7] above, wherein the stabilizer is a free radical stabilizer.
[9] The method according to any one of [1] to [8] above, wherein the light reflecting material component contains a particulate light reflecting material.
[10] The method according to any one of [1] to [9] above, wherein the photopolymerizable composition further contains an activator.
[11] The method according to any one of [1] to [10] above, further comprising a secondary curing step including a step of curing the printed matter.
[12] The method according to any one of the above [1] to [11], further comprising a step of rinsing the printed matter.
[13] The method according to any one of [1] to [12] above, wherein the photopolymerizable composition further contains a dye.
[14] Any of the above [1] to [13], wherein the photopolymerizable macromer component contains a monomer having an ethylenically unsaturated group or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group. The method described in paragraph 1.
[15] The method according to any one of [1] to [13] above, wherein the photopolymerizable macromer component contains a monomer having a thiol group or a macromer having a monomer unit (monomer) having a thiol group. ..
[16] The photopolymerizable macromer component is a monomer having an ethylenically unsaturated group, a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, a monomer having a thiol group, or a monomer having a thiol group. The method according to any one of the above [1] to [13], which comprises a macromer having a unit (monomer).
[17] The photopolymerizable macromer component is a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholin-2,5-dione, or The method according to any one of [1] to [16] above, which comprises a macromer containing at least one monomer unit among these combinations.
[18] The method according to any one of [1] to [17] above, wherein the light wavelength used for photopolymerization is 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700).
[19] The item according to any one of [1] to [18] above, wherein the photopolymerizable composition photopolymerizes under the same polymerization conditions in a shorter time than the photopolymerizable composition containing no reflective material. The method described.
[20] The photopolymerizable composition photopolymerizes under the same polymerization conditions at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition containing no reflective material. ] To [19]. The method according to any one of the following items.
[21] The method according to any one of the above [1] to [20], wherein the concentration range of the photoinitiator component is about 0.01 to about 5.0% by mass.
[22] The method according to [1] above, wherein at least one photoinitiator absorbs at a wavelength reflected by at least one light reflecting material.
[23] The method according to the above [1], wherein the curing depth is less than 150 microns.
[24] The method according to the above [1], wherein the light reflecting material component constitutes about 5 to about 90% by mass of the photopolymerizable composition.
[25] The method according to the above [1], wherein the light reflecting material component contains a particulate light reflecting material having a size of less than 500 microns.
[26] The method according to the above [1], wherein the light reflecting material component comprises a light reflecting material containing an organic compound, an inorganic compound, or a combination thereof.
[27] The method according to the above [1], wherein the light reflecting material component contains a light reflecting material which is a liquid.
[28] The method according to the above [1], wherein the light reflecting material component comprises a light reflecting material which is a polymer.
[29] The method according to [1] above, wherein the light-reflecting material component comprises a light-reflecting material that is or is not absorbent under physiological conditions.
[30] A polymer polymerized by the method according to any one of the above [1] to [29].
[31] An article produced by the method according to any one of the above [1] to [30].
[32] The article according to the above [31], which is a medical device.
[33] A non-toxic polymer article comprising a photopolymerizable biodegradable polymer and a non-toxic amount of a photoinitiator.
[34] A non-toxic polymer composition comprising a photopolymerized macromer and a non-toxic amount of a photoinitiator.
[35] The composition according to the above [34], further comprising a photopolymerized light-reflecting material.
[36] A photopolymerizable composition.
i) At least one photopolymerizable macromer component;
ii) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition; and
iii) At least one photoinitiator component
A photopolymerizable composition that adjusts the dose requirement of the photopolymerizable composition when the light-reflecting material component is compared to the dose requirement of the photopolymerizable composition that does not contain the light-reflecting material. thing.
[37] The above-mentioned [36], wherein the light-reflecting material component increases the polymerization rate on the surface of the photopolymerizable composition in contact with light as compared with the same photopolymerizable composition containing no light-reflecting material component. Composition.
[38] By incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a photoinitiator concentration lower than the concentration used in the photopolymerizable composition containing no light-reflecting material component. The composition according to the above [36].
[39] The composition according to the above [36], wherein the total concentration of the photoinitiator is less than 1.0% by mass.
[40] The composition according to [36] above, wherein the photopolymerizable composition further comprises a reactive or non-reactive diluent, or both.
[41] The composition according to any one of [36] to [40] above, wherein the photopolymerizable composition further contains a stabilizer.
[42] The composition according to the above [36], wherein the light-reflecting material component comprises a particulate light-reflecting material.
[43] The composition according to the above [36], wherein the photopolymerizable composition further contains an activator.
[44] The composition according to the above [43], wherein the light reflecting material component contains an activator.
[45] The composition according to the above [43], wherein the light reflecting material is an activator.
[46] The composition according to the above [43], wherein the light reflecting material contains an activator.
[47] The composition according to the above [43], wherein the photopolymerizable macromer component contains an activator.
[48] The composition according to the above [43], wherein the photopolymerizable macromer contains an activator.
[49] The composition according to [43] above, wherein the reactive diluent comprises the active agent.
[50] The composition according to [43] above, wherein the non-reactive diluent comprises the active agent.
[51] The composition according to any one of [36] to [50] above, wherein the photopolymerizable composition further contains a dye.
[52] The photopolymerizable macromer component is a monomer having an ethylenically unsaturated group, a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, a monomer having a thiol group, or a monomer having a thiol group. A macromer having a unit (monomer) or a monomer having an ethylenically unsaturated group, or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, and a monomer having a thiol group or a monomer unit having a thiol group ( The composition according to any one of [36] to [51] above, which comprises a combination with a macromer having a monomer).
[53] The photopolymerizable macromer component is a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholin-2,5-dione, or The composition according to any one of [36] to [52] above, which comprises a macromer containing at least one monomer unit of these combinations.
[54] Any of the above [36] to [53], wherein the photopolymerizable composition polymerizes when exposed to a light wavelength of 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700). The composition according to one item.
[55] The item according to any one of [36] to [54] above, wherein the photopolymerizable composition photopolymerizes under the same polymerization conditions in a shorter time than the photopolymerizable composition containing no reflective material. The composition described.
[56] The item according to any one of [36] to [55] above, wherein the photopolymerizable composition photopolymerizes under the same polymerization conditions in a shorter time than the photopolymerizable composition containing no reflective material. The composition described.
[57] The photopolymerizable composition photopolymerizes under the same polymerization conditions at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition containing no reflective material. ] To [56]. The composition according to any one of.
[58] The photopolymerizable composition photopolymerizes under the same polymerization conditions at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition containing no reflective material. ] To [57]. The composition according to any one of.
[59] The composition according to any one of [36] to [58], wherein the light initiator absorbs at a wavelength reflected by the light reflecting material.
[60] The composition according to any one of the above [36] to [59], wherein the light reflecting material component constitutes about 5 to about 65% by mass of the photopolymerizable composition.
[61] The composition according to any one of [36] to [60] above, wherein the light-reflecting material component comprises a light-reflecting material that is or is not absorbent under physiological conditions.
[62] Any of the above [36] to [61], wherein the light-reflecting material component comprises a photopolymerizable macromer, a diluent, a light-reflecting material, or a light-reflecting material that polymerizes with at least one of a combination thereof. The composition according to item 1.
[63] A stereolithographic photopolymerizable composition.
i) At least one photopolymerizable macromer component;
ii) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition; and
iii) At least one photoinitiator component
A stereolithographic photopolymerizable composition that adjusts the dose requirement of the composition when the light-reflecting material component is compared to the dose requirement of the composition that does not contain the light-reflecting material.
[64] A photopolymerizable composition for producing a continuous liquid interface.
i) At least one photopolymerizable macromer component;
ii) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition; and
iii) At least one photoinitiator component
A photopolymerizable composition for continuous liquid interface production, wherein the light-reflecting material component adjusts the dose requirement of the composition when compared with the dose requirement of the composition not containing the light-reflecting material. ..
[65] A DLP (Digital Light Processing) photopolymerizable composition.
i) At least one photopolymerizable macromer component;
ii) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition; and
iii) At least one photoinitiator component
A DLP photopolymerizable composition comprising the light-reflecting material component to adjust the dose requirement of the composition when compared to the dose requirement of the composition not comprising the light-reflecting material.
[66] A photopolymerizable ink composition.
a) At least one photopolymerizable macromer component;
b) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition;
c) At least one photoinitiator component;
d) Reactive diluent; and
e) Stabilizer
A photopolymerizable ink that adjusts the dose requirement of the photopolymerizable composition when the light-reflecting material component is compared to the dose requirement of the photopolymerizable composition that does not contain the light-reflecting material. Composition.
[67] A photopolymerizable ink composition.
a) At least one photopolymerizable macromer component;
b) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition;
c) At least one photoinitiator component;
d) Reactive diluent; and
e) Stabilizer
A photopolymerizable ink composition that adjusts the dose requirement of the photopolymerizable composition when the light-reflecting material component is compared to the dose requirement of the composition that does not contain the light-reflecting material.
[68] When added to a photopolymerizable ink formulation of a light-reflecting material, the irradiation dose requirement of the ink formulation is compared with the irradiation dose requirement of the ink formulation that does not contain the light-reflecting material. Includes at least one of an inorganic solid, an organic compound, a crystalline organic compound, a crystalline amino acid and / or a derivative thereof, a crystalline fatty acid and / or a derivative thereof, a crystalline peptide, or a combination thereof so as to be adjusted. , Light reflective material.
[69] The inorganic compound is titanium dioxide, zinc oxide, barium sulfate, tricalcium phosphate, dicalcium phosphate, monocalcium phosphate, dicalcium diphosphate, calcium triphosphate, hydroxyapatite, apatite, and tetracalcium phosphate. , Or a combination thereof, according to the above [68].
[70] The organic compound is polyester, polyurethane, polyether, polyanhydride, polyamide, polycarbonate, polyketone, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyimide, and polyhydroxyalkanoate, or The material according to [68] above, which comprises an aliphatic polymer and a copolymer of these combinations.
[71] The material according to [68] above, wherein the organic compound comprises a polyester, a polyurethane, a polyether, a polyanhydrous, a polyketone, a polyamide, a polycarbonate, and a polyimide, or an aromatic polymer and a copolymer of a combination thereof.
[72] The organic compound is cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin 50, amylose, glucan, heparin. , Xylan, pectin, galactan, glycosaminoglycan, dextran, amination dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfate polysaccharide, mucopolysaccharide, gelatin, zein, collagen, alginic acid, agar , Caraginan, guar gum, arabic gum, gati gum, karaya gum, konjak gum, tamarind gum, tara gum, polysaccharide gum, locust bean gum, pectin, xanthan gum, or combinations thereof, comprising naturally derived polymers and derivatives thereof, according to the above [68]. material.
[73] The material according to the above [68], wherein the crystalline organic compound contains a crystalline aliphatic and aromatic polymer, and a combination thereof.
[74] The material according to the above [68], wherein the crystalline organic compound contains a crystalline naturally derived polymer and a derivative, and a combination thereof.
[75] The material according to the above [68], which comprises crystalline amino acids, derivatives thereof, and combinations thereof.
[76] The material according to the above [68], wherein the crystalline fatty acid comprises palmitic acid, ascorbyl palmitate, lauric acid, monolauric acid glycerol, myristic acid, capric acid, and a combination thereof.
Claims (15)
ａ）光重合性組成物を一時的に光に暴露する工程であって、前記光重合性組成物が、
ｉ．少なくとも１種の光重合性マクロマー成分；
ｉｉ．前記光重合性組成物中に懸濁した少なくとも１種の光反射材料成分；及び
ｉｉｉ．少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、工程、並びに
ｂ）少なくとも重合マクロマーを含む印刷物を形成する工程
を含む、方法。 It is a method of photopolymerization printing of articles.
a) A step of temporarily exposing the photopolymerizable composition to light, wherein the photopolymerizable composition is:
i. At least one photopolymerizable macromer component;
ii. At least one light-reflecting material component suspended in the photopolymerizable composition; and iii. The light-reflecting material component adjusts the dose requirement of the photopolymerizable composition when compared to the dose requirement of the composition containing at least one photoinitiator component and not containing the light-reflecting material. , And b) a method comprising the step of forming a printed matter containing at least a polymerization macromer.
ａ）少なくとも１種の光重合性マクロマー成分；
ｂ）前記光重合性組成物中に懸濁した光反射材料を含む少なくとも１種の光反射材料成分；及び
ｃ）少なくとも１種の光開始剤成分
を含み、前記光反射材料成分が、前記光反射材料を含まない光重合性組成物の照射量要件と比較した場合に、前記光重合性組成物の照射量要件を調整する、光重合性組成物。 It is a photopolymerizable composition
a ) At least one photopolymerizable macromer component;
b ) At least one light-reflecting material component, including a light-reflecting material suspended in the photopolymerizable composition; and
c ) Irradiation of the photopolymerizable composition when the light-reflecting material component contains at least one photoinitiator component and is compared to the dose requirement of the photopolymerizable composition without the light-reflecting material. A photopolymerizable composition that adjusts the quantity requirements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2023158228A JP2023181163A (en) | 2018-04-06 | 2023-09-22 | Method and composition for photopolymerizable additive manufacturing |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201862653584P | 2018-04-06 | 2018-04-06 | |
| US62/653,584 | 2018-04-06 | ||
| PCT/US2019/026114 WO2019195763A1 (en) | 2018-04-06 | 2019-04-05 | Methods and compositions for photopolymerizable additive manufacturing |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023158228A Division JP2023181163A (en) | 2018-04-06 | 2023-09-22 | Method and composition for photopolymerizable additive manufacturing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2021521285A JP2021521285A (en) | 2021-08-26 |
| JPWO2019195763A5 true JPWO2019195763A5 (en) | 2022-03-10 |
Family
ID=68101126
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020554897A Pending JP2021521285A (en) | 2018-04-06 | 2019-04-05 | Methods and Compositions for Photopolymerizable Addition Production |
| JP2023158228A Pending JP2023181163A (en) | 2018-04-06 | 2023-09-22 | Method and composition for photopolymerizable additive manufacturing |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2023158228A Pending JP2023181163A (en) | 2018-04-06 | 2023-09-22 | Method and composition for photopolymerizable additive manufacturing |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20210155722A1 (en) |
| EP (2) | EP3774338B1 (en) |
| JP (2) | JP2021521285A (en) |
| CN (2) | CN112166039B (en) |
| CA (1) | CA3096216A1 (en) |
| WO (1) | WO2019195763A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4289607A3 (en) | 2017-07-28 | 2024-03-06 | Stratasys Ltd. | Method and system for fabricating object featuring properties of a hard tissue |
| US11559936B2 (en) | 2017-07-28 | 2023-01-24 | Stratasys Ltd. | Additive manufacturing processes employing a material featuring properties of a soft bodily tissue |
| JP7329498B2 (en) | 2017-07-28 | 2023-08-18 | ストラタシス リミテッド | Methods and systems for fabricating objects with vascular properties |
| WO2019021293A1 (en) * | 2017-07-28 | 2019-01-31 | Stratasys Ltd. | Formulations usable in additive manufacturing of a three-dimensional object made of a soft material |
| JP7438129B2 (en) * | 2018-04-19 | 2024-02-26 | ポリ－メッド インコーポレイテッド | Macromers and compositions for photocuring processes |
| WO2021055458A1 (en) * | 2019-09-16 | 2021-03-25 | Carbon, Inc. | Bio absorbable resin for additive manufacturing |
| WO2022232579A1 (en) * | 2021-04-29 | 2022-11-03 | University Of Pittsburgh-Of The Commonwealth System Of Higher Education | Method and system of flow bed assisted photopolymerization based additive manufacturing (fb-pam) |
| WO2022271904A1 (en) * | 2021-06-24 | 2022-12-29 | Poly-Med, Inc. | Methods and compositions comprising chain transfer agents in absorbable photopolymerizable formulations |
| US11952457B2 (en) | 2021-06-30 | 2024-04-09 | Carbon, Inc. | Bioabsorbable resin for additive manufacturing with non-cytotoxic photoinitiator |
| WO2024084040A1 (en) * | 2022-10-20 | 2024-04-25 | Cellink Bioprinting Ab | An aqueous bioink solution for use in light-based bioprinting applications, and methods of using the aqueous bioink solution |
Family Cites Families (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223040A (en) * | 1974-11-26 | 1980-09-16 | Carroll John M | Lauric acid for the prevention and treatment of mycobacterial diseases |
| EP0210637B1 (en) * | 1985-07-31 | 1991-09-11 | E.I. Du Pont De Nemours And Company | Optical coating composition |
| JP2613929B2 (en) * | 1988-10-19 | 1997-05-28 | 松下電工株式会社 | Method and apparatus for forming a three-dimensional shape |
| JP3220968B2 (en) * | 1994-08-26 | 2001-10-22 | 花王株式会社 | Transparent liquid hair styling composition |
| US5744148A (en) * | 1996-09-20 | 1998-04-28 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Stabilization of an unstable retinoid in oil-in-water emulsions for skin care compositions |
| USRE38722E1 (en) * | 1997-02-19 | 2005-04-12 | Ultradent Products, Inc. | Polymerizable isolation barriers containing reflective materials and methods for forming and using such barriers |
| US6305936B1 (en) * | 1997-02-19 | 2001-10-23 | Ultradent Products, Inc. | Polymerizable isolation barriers with reduced polymerization strength and methods for forming and using such barriers |
| US6200646B1 (en) * | 1999-08-25 | 2001-03-13 | Spectra Group Limited, Inc. | Method for forming polymeric patterns, relief images and colored polymeric bodies using digital light processing technology |
| JP2001213908A (en) * | 1999-11-11 | 2001-08-07 | Mitsubishi Chemicals Corp | Ultraviolet curing resin composition and recording material for ink jet having film based on the composition |
| JP4141120B2 (en) * | 2001-08-16 | 2008-08-27 | 富士フイルム株式会社 | Master for lithographic printing plate |
| JP2005515221A (en) * | 2002-01-07 | 2005-05-26 | アボット ゲーエムベーハー ウント カンパニー カーゲー | Amino acid crystallization using ultrasonic shaking |
| JP4214729B2 (en) * | 2002-07-25 | 2009-01-28 | コニカミノルタホールディングス株式会社 | Curable white ink composition |
| JP2005055682A (en) * | 2003-08-05 | 2005-03-03 | Canon Inc | Manufacturing method for light quantity adjusting member, light quantity adjusting member, light quantity adjusting device and photographing device |
| KR100705624B1 (en) * | 2003-12-24 | 2007-04-11 | 비오이 하이디스 테크놀로지 주식회사 | Method for fabricating reflective type LCD |
| US8821559B2 (en) * | 2004-08-27 | 2014-09-02 | Codman & Shurtleff, Inc. | Light-based implants for treating Alzheimer's disease |
| EP2050720A1 (en) * | 2007-10-16 | 2009-04-22 | Mondi Business Paper Services AG | Laser and thermally writable surface coating for materials |
| JP5415029B2 (en) * | 2008-07-01 | 2014-02-12 | 株式会社リコー | UV curable ink jet recording ink and color image forming apparatus |
| US20120259031A1 (en) * | 2009-12-17 | 2012-10-11 | Dsm Ip Assets, B.V. | Led curable liquid resin compositions for additive fabrication |
| US20110160321A1 (en) * | 2009-12-30 | 2011-06-30 | Steven Ray Merrigan | Reduction of unpolymerized monomers in high internal phase emulsion foam |
| CN102005532A (en) * | 2010-10-15 | 2011-04-06 | 陈林 | High-efficiency reflective LED package structure and packaging method thereof |
| US8851649B2 (en) * | 2011-05-13 | 2014-10-07 | Eckart Gmbh | UV ink jet printing ink composition |
| JP2013018920A (en) * | 2011-07-13 | 2013-01-31 | Seiko Epson Corp | Ink set and recorded matter |
| WO2013146081A1 (en) * | 2012-03-30 | 2013-10-03 | 出光興産株式会社 | Resin composition, cured product of same, and reflective material for optical semiconductors using said cured product |
| EP3203318A1 (en) * | 2013-02-12 | 2017-08-09 | CARBON3D, Inc. | Continuous liquid interphase printing |
| US20150002926A1 (en) * | 2013-06-27 | 2015-01-01 | Motorola Mobility Llc | Reflective Mold Apparatus and Methods for UV Curing |
| JP6493227B2 (en) * | 2014-02-07 | 2019-04-03 | 堺化学工業株式会社 | Hexagonal plate-like zinc oxide particles, method for producing the same, cosmetics, filler, resin composition, infrared reflector, and coating composition |
| GB201409451D0 (en) * | 2014-05-28 | 2014-07-09 | Ipabc Ltd | Antimicrobial preparations, methods for preparing the same and uses thereof to combat microorganisms |
| CN106459760A (en) * | 2014-06-20 | 2017-02-22 | 米兰集团 | Lithographic printing plates precursors comprising a radiation sensitive imageable layer with a crosslinked surface |
| JP6720092B2 (en) * | 2014-06-23 | 2020-07-08 | カーボン，インコーポレイテッド | Method for manufacturing polyurethane three-dimensional object from materials having various curing mechanisms |
| CN104369496B (en) * | 2014-11-02 | 2016-09-07 | 合肥乐凯科技产业有限公司 | A kind of heat-ultraviolet light for in-mold decoration double solidification hardening film |
| EP3305508B1 (en) * | 2015-06-08 | 2020-10-21 | FUJIFILM Corporation | Actinic ray-curable-type inkjet ink set for three-dimensional printing, three-dimensional printing method, and three-dimensional printing system |
| JP6819671B2 (en) * | 2016-03-18 | 2021-01-27 | 株式会社リコー | Active energy ray-curable composition, manufacturing method of three-dimensional model, and manufacturing equipment for three-dimensional model |
| CN106818334B (en) * | 2016-12-29 | 2020-07-14 | 杭州福斯特应用材料股份有限公司 | High-reflection degradable mulching film |
| KR101822151B1 (en) * | 2017-06-28 | 2018-01-25 | 비즈텍코리아 주식회사 | Photocurable polysiloxane composition for 3D printing and dental model comprising the same |
-
2019
- 2019-04-05 EP EP19781362.9A patent/EP3774338B1/en active Active
- 2019-04-05 US US17/045,672 patent/US20210155722A1/en active Pending
- 2019-04-05 JP JP2020554897A patent/JP2021521285A/en active Pending
- 2019-04-05 EP EP23183272.6A patent/EP4257628A3/en active Pending
- 2019-04-05 CA CA3096216A patent/CA3096216A1/en active Pending
- 2019-04-05 CN CN201980035713.2A patent/CN112166039B/en active Active
- 2019-04-05 WO PCT/US2019/026114 patent/WO2019195763A1/en active Application Filing
- 2019-04-05 CN CN202311068173.2A patent/CN117001995A/en active Pending
-
2023
- 2023-09-22 JP JP2023158228A patent/JP2023181163A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112166039B (en) | Methods and compositions for photopolymerized additive manufacturing | |
| JP2023181163A5 (en) | ||
| Yu et al. | Injectable hydrogels as unique biomedical materials | |
| Buwalda et al. | Hydrogels in a historical perspective: From simple networks to smart materials | |
| US7144976B2 (en) | Coumarin endcapped absorbable polymers | |
| Tomihata et al. | Preparation of cross-linked hyaluronic acid films of low water content | |
| Tikhonov et al. | Stereolithographic fabrication of three-dimensional permeable scaffolds from CaP/PEGDA hydrogel biocomposites for use as bone grafts | |
| US7511083B2 (en) | Hydrogel | |
| JPWO2019195763A5 (en) | ||
| CA2634245C (en) | Light-curable bone growth material for treating dental bone defects | |
| Fattahpour et al. | An injectable carboxymethyl chitosan-methylcellulose-pluronic hydrogel for the encapsulation of meloxicam loaded nanoparticles | |
| US20110136935A1 (en) | Bone and/or dental cement composition and uses thereof | |
| CA2430130A1 (en) | Polyalkylene glycol viscosity-enhancing polymeric formulations | |
| Chan et al. | Functionalizable hydrogel microparticles of tunable size and stiffness for soft-tissue filler applications | |
| CA2810590A1 (en) | Mercapto-modified biocompatible macromolecule derivatives with low degree of mercapto-modification and the cross-linked materials and uses thereof | |
| Zhou et al. | Visible light-curable polymers for biomedical applications | |
| Iftime et al. | New formulations based on salicyl-imine-chitosan hydrogels for prolonged drug release | |
| MXPA01005338A (en) | Nitric oxide-producing hydrogel materials. | |
| JP6362614B2 (en) | Absorbents and biocompatible reflective dyes for high precision medical implants | |
| Mawad et al. | Network structure and macromolecular drug release from poly (vinyl alcohol) hydrogels fabricated via two crosslinking strategies | |
| US20210388232A1 (en) | Curable Polymeric Compositions | |
| Abbondandolo et al. | Assessing the degradation profiles of a thermoresponsive polyvinyl alcohol (PVA)‐based hydrogel for biomedical applications | |
| JP3825411B2 (en) | Malic acid hydrogel | |
| Iftime et al. | Green Open Access: Authors’ Self-archive manuscript (enabled to public access on November 2021, after 12 month embargo period) | |
| Bao et al. | Degradable polymer bone adhesives |