EP3661974A1 - Composition photopolymérisable, matériau obtenu par polymérisation d'une telle composition et procédé d'impression 3d utilisant une telle composition - Google Patents
Composition photopolymérisable, matériau obtenu par polymérisation d'une telle composition et procédé d'impression 3d utilisant une telle compositionInfo
- Publication number
- EP3661974A1 EP3661974A1 EP18752608.2A EP18752608A EP3661974A1 EP 3661974 A1 EP3661974 A1 EP 3661974A1 EP 18752608 A EP18752608 A EP 18752608A EP 3661974 A1 EP3661974 A1 EP 3661974A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- annihilator
- photosensitizer
- molecule
- composition
- photoinitiator
- 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 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 230000005284 excitation Effects 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 230000007246 mechanism Effects 0.000 claims abstract description 31
- 238000012546 transfer Methods 0.000 claims abstract description 20
- 238000010146 3D printing Methods 0.000 claims abstract description 11
- 239000003504 photosensitizing agent Substances 0.000 claims description 104
- 238000010521 absorption reaction Methods 0.000 claims description 40
- 239000003963 antioxidant agent Substances 0.000 claims description 22
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 claims description 13
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001454 anthracenes Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 7
- CNRNYORZJGVOSY-UHFFFAOYSA-N 2,5-diphenyl-1,3-oxazole Chemical compound C=1N=C(C=2C=CC=CC=2)OC=1C1=CC=CC=C1 CNRNYORZJGVOSY-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000008033 biological extinction Effects 0.000 claims description 6
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 claims description 4
- YDYTTZZBQVZTPY-UHFFFAOYSA-N 2-chloro-9,10-bis(phenylethynyl)anthracene Chemical compound C=12C=CC=CC2=C(C#CC=2C=CC=CC=2)C2=CC(Cl)=CC=C2C=1C#CC1=CC=CC=C1 YDYTTZZBQVZTPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000002118 epoxides Chemical class 0.000 claims description 4
- UXGVMFHEKMGWMA-UHFFFAOYSA-N 2-benzofuran Chemical class C1=CC=CC2=COC=C21 UXGVMFHEKMGWMA-UHFFFAOYSA-N 0.000 claims description 3
- NWCLERWRYGAIPF-UHFFFAOYSA-N 2-chloro-9,10-dinaphthalen-1-ylanthracene Chemical compound Clc1ccc2c(-c3cccc4ccccc34)c3ccccc3c(-c3cccc4ccccc34)c2c1 NWCLERWRYGAIPF-UHFFFAOYSA-N 0.000 claims description 3
- PGBFVDVTXFHOHV-UHFFFAOYSA-N 2-methyl-9,10-dinaphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=C(C=4C5=CC=CC=C5C=CC=4)C4=CC=C(C=C43)C)=CC=CC2=C1 PGBFVDVTXFHOHV-UHFFFAOYSA-N 0.000 claims description 3
- ZHBOFZNNPZNWGB-UHFFFAOYSA-N 9,10-bis(phenylethynyl)anthracene Chemical compound C1=CC=CC=C1C#CC(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C#CC1=CC=CC=C1 ZHBOFZNNPZNWGB-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- PIPBVABVQJZSAB-UHFFFAOYSA-N bis(ethenyl) benzene-1,2-dicarboxylate Chemical compound C=COC(=O)C1=CC=CC=C1C(=O)OC=C PIPBVABVQJZSAB-UHFFFAOYSA-N 0.000 claims description 3
- AJCHRUXIDGEWDK-UHFFFAOYSA-N bis(ethenyl) butanedioate Chemical compound C=COC(=O)CCC(=O)OC=C AJCHRUXIDGEWDK-UHFFFAOYSA-N 0.000 claims description 3
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 claims description 3
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000004643 cyanate ester Substances 0.000 claims description 3
- 150000001913 cyanates Chemical class 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
- DWOJCOPNWVOIHM-UHFFFAOYSA-N platinum(2+) 2,11,20,29-tetraphenyl-37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene Chemical compound [Pt+2].C1=CC=CC=C1C(C=1NC(=C2C=CC=CC2=1)C(C=1C=CC=CC=1)=C1N=C(C2=CC=CC=C21)C(C=1C=CC=CC=1)=C1NC(C2=CC=CC=C21)=C1C=2C=CC=CC=2)=C2C3=CC=CC=C3C1=N2 DWOJCOPNWVOIHM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 3
- KAPOSTKECKHKAP-UHFFFAOYSA-N st51006858 Chemical compound N1=C(N=C2C3=C(OCCCC)C=CC(OCCCC)=C3C(N=C3N4)=N2)[C]2C(OCCCC)=CC=C(OCCCC)C2=C1N=C(N1)C2=C(OCCCC)C=CC(OCCCC)=C2C1=NC4=C1[C]3C(OCCCC)=CC=C1OCCCC KAPOSTKECKHKAP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- JTGMTYWYUZDRBK-UHFFFAOYSA-N 9,10-dimethylanthracene Chemical compound C1=CC=C2C(C)=C(C=CC=C3)C3=C(C)C2=C1 JTGMTYWYUZDRBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 claims description 2
- 238000000206 photolithography Methods 0.000 claims description 2
- 230000001131 transforming effect Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 2
- PDZNVMMBPXRXQV-UHFFFAOYSA-N 1-methyl-9,10-dinaphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C(C=4C5=CC=CC=C5C=CC=4)=C4C=CC=C(C=34)C)=CC=CC2=C1 PDZNVMMBPXRXQV-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 14
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 12
- 229930006711 bornane-2,3-dione Natural products 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910001882 dioxygen Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000003211 polymerization photoinitiator Substances 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000004424 polypyridyl Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CUFJSCZIPZFGJA-UHFFFAOYSA-N 1,4-diphenyl-2-benzofuran Chemical compound C=12C=CC=C(C=3C=CC=CC=3)C2=COC=1C1=CC=CC=C1 CUFJSCZIPZFGJA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- GWNJZSGBZMLRBW-UHFFFAOYSA-N 9,10-dinaphthalen-1-ylanthracene Chemical compound C12=CC=CC=C2C(C=2C3=CC=CC=C3C=CC=2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 GWNJZSGBZMLRBW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 208000017983 photosensitivity disease Diseases 0.000 description 1
- 231100000434 photosensitization Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
- G03F7/2055—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser for the production of printing plates; Exposure of liquid photohardening compositions
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Definitions
- Photopolymerizable composition material obtained by polymerization of such a composition and 3D printing method using such a composition
- the invention relates to the field of three-dimensional printing of objects by photopolymerization of a resin, and more precisely in this field, a photopolymerizable composition, a material obtained by photopolymerization of such a composition and a 3D printing process using a such composition.
- 3D microfabrication based on photopolymerization induced by multiphoton absorption is a technique invented in the 1990s, based on the non-linear absorption of photosensitizers. This technique is described in particular in US8197722, US20040067451 or US20110021653. This technique is very effective for three-dimensional printing of objects. But it leads to a localized photopolymerization only at the focal point, that is to say a light curing limited to volumes of very small dimensions with submicron spatial resolution; the use of this particularly slow technique is limited to the realization of objects of small dimensions, of the order of a millimeter. It also requires particularly powerful pulsed lasers, having an irradiance typically of the order of magnitude of TWatt / cm 2 .
- a non-linear photosensitization technique based on a fluorescence up-conversion mechanism of inorganic materials has also been developed to excite polymerization photoinitiators suitable for radical generation (for radical polymerization) or acids (for cationic polymerization).
- This technique is described in particular in document US20040198857. This technique makes it possible to use lasers having an irradiance of about MWatt / cm 2 , which remains high.
- the massively parallel manufacturing approach by simultaneous projection of multiple laser spots can exceed the contradiction between resolution and manufacturing speed. It is commonly used with 3D printers that use mask projection, including high resolution micro-stereolithography systems. In these cases the photopolymerization is triggered by a simultaneous single photon absorption of several million laser spots, which correspond to the pixels of the projected image.
- the axial resolution is obtained by a mechanical means for renewing the photopolymer between each layer, which imposes a minimum thickness, typically from 5 to 10 microns. This is to be compared with multiphoton absorption photopolymerization for which the axial resolution, determined by the optical thickness of the projected image in the volume of the resin, is very easily submicron.
- PCT / EP2016079661 discloses an inhomogeneous material comprising optical conversion components, liquid form components entrapped in a photopolymerized resin matrix.
- the polymerization of the resin is initiated by a direct action of an external light signal on a polymerization photoinitiator, which has no effect on the components for optical conversion.
- the material obtained makes it possible to protect said components, in particular from a degradation of their properties by the ambient oxygen.
- the "Low-Threshold Photon Upconversion Capsules Obtained by Photoinduced Interfacial Polymerization" document by J-Hwan Kang and Eisa Reichmanis describes a similar material obtained under similar conditions.
- This document describes a material comprising components for optical conversion, oily liquid phase components trapped in a photopolymerized resin bubble.
- the polymerization of the resin is initiated by a direct action of an external light signal on an aqueous liquid composition comprising a resin and a polymerization photoinitiator, which has no effect on the components for optical conversion.
- the invention proposes a novel non-linear photopolymerizable composition in continuous and ultra-sensitive light irradiance, as an alternative to photopolymerizable multiphoton compositions, especially when the manufacturing processes require the projection of 2D or 3D distributions of irradiances, for example comprising numerous laser spots in the composition.
- a novel photopolymerizable composition comprising at least:
- a photoinitiator the photosensitizer being capable of absorbing an excitation light signal received in a first wavelength range, the annihilator being capable of emitting a light signal in a second wavelength range different from the first wavelength range, wherein, upon absorption of light by the photosensitizer in said first wavelength range, the annihilator emits a light signal in the second wavelength range, a photonic energy of the light signal emitted by the annihilator being greater than a photonic energy of the light signal received by the photosensitizer, wherein the annihilator is capable of implementing a mechanism of energy transfer to excite the photoinitiator of polymerization of the resin, and wherein the excited photoinitiator is capable of generating at least one polymerization initiator capable of causing a polymerization reaction of the resin.
- the invention thus proposes a photopolymerizable composition, not directly by the action of the excitation signal received, as is the case with the previous compositions, but indirectly by the action the light signal emitted by the annihilator.
- the received excitation light signal whose wavelength is in the first range of lengths of wavelength. wave, has no action on the photoinitiator.
- the photoinitiator reacts against the effect of the light signal emitted by the annihilator whose central wavelength is in the second range of wavelengths.
- the photonic energy of the light signal emitted by the annihilator is greater than the photonic energy of the light signal received by the photosensitizer, it becomes possible to photoplymerise the resin under much more advantageous conditions, by using a light signal.
- light excitation whose energy is lower than the energy of the signals which it is necessary to use in the previous solutions.
- the photosensitizer and the annihilator are capable of implementing together an absorption reaction, by the photosensitizer, of two photons of the light excitation signal, followed by an additive conversion reaction of triplet annihilation energy (STTA-UC) to obtain an excited annihilator whose photon energy over the second wavelength range is greater than the photon energy of the excitation signal.
- the excited annihilator and the photoinitiator are capable of implementing a mechanism of energy transfer between said annihilator and said photoinitiator to produce an excited photoinitiator capable of generating at least one polymerization initiator capable of causing a polymerization reaction of the resin .
- the mechanism of energy transfer between the annihilator and the photosensitizer can be for example by emission / absorption of a secondary signal whose photon energy is greater than the photonic energy of the excitation signal or by resonant transfer of energy.
- the annihilator may also be the photoinitiator and may, if appropriate, directly generate a polymerization initiator after having been excited.
- the invention thus proposes a composition that is particularly sensitive to external irradiations, adapted to be polymerized by the implementation of an efficient STTA-UC mechanism with irradiances of the order of the irradiance of the sun, that is to say say of the order of 0.1 W / cm 2 , much lower than the necessary irradiances with known prior art.
- the STTA-UC mechanism the effectiveness of which is nonlinear in irradiance, makes it possible to obtain confined photopolymerization in controlled three-dimensional radiation zones and with continuous light sources.
- the photosensitizer (PS) comprises at least one molecule capable of passing from a singlet state to a triplet state when it absorbs the photonic energy of the external excitation signal.
- the annihilator (AN) comprises molecules capable of:
- the photopolymerizable resin may comprise monomers, oligomers or radical polymerizable polymers or by addition or crosslinking mechanisms such as:
- acrylated monomers such as acrylates, polyacrylates, methacrylates, for example a pentaerythritol triacrylate, a polyethylene glycol diacrylate or an acrylate such as aronix D-800 marketed by the company TAOGOSEI Ltd. or
- acrylated oligomers such as unsaturated amides, or
- methacrylated polymers polymers which have a hydrocarbyl backbone and pendant peptide groups with a free radical polymerizable functionality, or
- vinyl compounds such as styrenes, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate, or
- the resin may comprise cationically polymerizable monomers and oligomers and cationically crosslinkable polymers, for example epoxy resins such as monomeric epoxides and polymeric epoxides having one or more epoxy groups, vinyl ethers, cyanate esters, and mixtures of several of these compounds.
- the photosensitizer, the annihilator, and a photoinitiator, as well as the mechanism used for the polymerization will be detailed below.
- the composition according to the invention may also comprise an antioxidant.
- the photosensitizer, the annihilator and / or the photoinitiator may have antioxidant properties.
- An antioxidant makes it possible to limit the harmful effect of dissolved oxygen in the composition.
- the molecular oxygen dissolved in the resin deactivates molecules in the triplet state ("3PS *", "3AN *” and "3PI *") very quickly and reduces their lifetime.
- the presence of molecular oxygen in the resin may decrease triplet-triplet energy transfer efficiency and annihilation triplet-triplet, finally it can prevent photoinitiation or reduce its effectiveness.
- this deactivation often induces the formation of singlet oxygen which can react with the components of the composition and impair their function.
- compositions within the scope of the invention may contain one or more chemical additives with antioxidant properties.
- methods can be used to reduce molecular oxygen-inhibiting effects, by reducing the molecular oxygen concentration before and / or during irradiation by the external light source as will be seen further below.
- the invention also relates to a process for the photopolymerization of a composition according to any one of the preceding claims, comprising a polymerizable resin, a photosensitizer, an annihilator and a photoinitiator, in which process:
- the photosensitizer absorbs a light signal received in a first wavelength range, and transfers the energy received from the light signal to the annihilator,
- the annihilator emits a light signal in a second wavelength range different from the first wavelength range, a photonic energy of the light signal emitted by the annihilator being greater a photonic energy of the light signal received by the photosensitizer,
- the annihilator transfers energy to the photoinitiator to excite the photoinitiator of polymerization of the resin
- the photoinitiator excited by the annihilator generates at least one polymerization initiator
- the polymerization initiator causes a polymerization reaction of the resin.
- the invention also relates to a material obtained by a photopolymerization process as described above, a composition according to the invention, including but not limited to a material having the shape of a thin-layered object such as a film or a three-dimensional solid object.
- the material obtained is homogeneous.
- the invention also relates to a three-dimensional printing process, comprising a step of transforming a volume of composition according to the invention by irradiation of said volume.
- the irradiation of the composition volume according to the invention to be light-cured can be carried out by an excitation source emitting an external excitation light signal of a power of less than 1000 W / cm 2 , preferably less than 1 W / cm 2 and even more preferably less than 0.1 W / cm 2 over the first range of wavelengths.
- a power much lower than the powers necessary for the implementation of existing techniques, allows to consider the development of 3D printing techniques on an industrial scale.
- the irradiation may for example be carried out by a three-dimensional photolithography technique, a three-dimensional holographic projection technique or a so-called direct laser writing technique (or “3D direct laser writing”). ").
- the method according to the invention may also comprise an initialization step during which oxygen molecules contained in the composition are eliminated.
- the irradiation of the composition volume can be carried out under a flow of inert gas, for example argon, nitrogen or carbon dioxide. This eliminates the inhibiting effects of oxygen.
- the invention finally relates to a use of a composition according to the invention in a three-dimensional printing device comprising a reservoir containing said composition and an external excitation light source capable of emitting a light signal in the first range. wavelengths and arranged to irradiate a predefined volume of composition within the reservoir, the irradiated volume having a thickness preferably of less than 1 cm.
- the optical excitation source comprises an optical system adapted to be immersed and moved in the liquid composition. This allows in particular to polymerize a composition thickness greater than 1 cm.
- the invention relates to a photopolymerizable composition
- a photopolymerizable composition comprising at least one photopolymerizable resin, a photosensitizer of PS triplets, an annihilator of triplets AN and a photoinitiator of polymerization Pl.
- the invention also relates to various procedures and additives adapted to reduce the inhibitory effect of molecular oxygen and thereby improve the efficiency of the polymerization process.
- Composition Example No. 1 Composition Example No. 1
- polymerizable resin a monomer of the acrylic acid ester type, more specifically an Aronix D-800 resin (TOAGOSEI CO. LTD),
- PS photosensitizer a porphyrin, more specifically an octaethylporphyrin platinum, commonly known as PtOEP
- anthracene derivative more specifically a 9,10-diphenylanthracene, commonly abbreviated DPA, and
- CQ Camphorquinone
- the concentrations of the various components have been chosen on the one hand to allow penetration of at least one millimeter of the composition of at least 50% of the energy of the excitation signal and secondly for obtain the implementation of an STTA-UC mechanism with an efficient quantum yield for the polymerization.
- the first length range of The waves may be between 520 and 550 nm, whose terminals are on either side of the central wavelength of the absorption spectrum of the photosensitizer
- the DPA annihilator does not absorb at the emission wavelengths of the PtOEP, nor at the 532 nm wavelength.
- the DPA emits efficiently at the wavelength of absorption of the photoinitiator CQ between 400 and 500 nm (second wavelength range): the experiment thus shows that the light power emitted by the DPA at 440 nm is This is a function of the square of the light power of the excitation source, which is characteristic of a high energy emission following the absorption of two photons by the STTA-UC mechanism.
- a concentration of 6 mM of DPA was used, a concentration 60 times greater than the concentration of photosensitizer PtOEP.
- DPA is also an antioxidant that helps reduce the limiting effects of molecular oxygen dissolved in the resin.
- the photoinitiator PI used camphorquinone, is a photoinitiator producing free radicals able to trigger a polymerization chain reaction.
- the CQ photoinitiator does not absorb green light at 532 nm, but absorbs in the blue between 400 and 500 nm (second wavelength range) and therefore absorbs the photons emitted by the annihilator AN. In the example used, a concentration of 0.5 mM PI was used.
- the selected resin is photopolymerizable by a radical-type mechanism, and able to react with the photoinitiator.
- the initiation of STTA-UC induced photopolymerization proceeds as follows.
- a light source illuminates the part of the composition to be polymerized by an excitation signal emitting on a first wavelength range corresponding to the PS absorption.
- a green laser emitting at 532 nm was used.
- Only the PS molecules in the example PtOEP) absorb photons at 532 nm and form predominantly triplet states "3PS *".
- these molecules "1AN *” transfer their energies to the molecules of the photoinitiator PI (in the example the CQ). This energy transfer can be done either by a non-radiative mechanism or by the emission of a secondary signal in a second range of lengths waveform (400-500 nm in the examples) different from the first range of wavelengths. Then, the photoinitiators PI generate radicals "R *” after conversion in their triplet states "3PI *". Finally, these "R” radicals cause the radical polymerization reaction of the monomers which constitute the base of the resin.
- the polymerization is limited to three-dimensional areas in which the irradiance of the excitation source has created enough radicals by the STTA-UC mechanism.
- the excitation signal was focused in a millimeter-thick composition layer according to the invention by a microscope objective to create a submicron sized polymerization voxel. The continuous displacement of the focusing point during the light excitation made it possible to manufacture polymerization lines inside the composition.
- the front face of a 3D hologram of the edges of an 8 mm side cube was projected into a composition tank with a thickness of about 1 mm; the polymerization of the resin made it possible to obtain a solid reproduction of this 3D image.
- Embodiment No. 2 The nonlinear polymerization initiated by the STTA-UC mechanism was obtained in a second practical example of a homogeneous composition according to the invention comprising: As polymerizable resin, an acrylate-type monomer, more specifically pentaerythriol triacrylate,
- PS photosensitizer a porphyrin, more specifically an octaethylporphyrin platinum, commonly known as PtOEP
- anthracene derivative more specifically a 9,10-diphenylanthracene, commonly abbreviated DPA, and
- phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide commonly abbreviated BAPO.
- the concentration of PtOEP was 8 ⁇ 1 , about 17-fold lower than in Example No.1, allowing a transmission of about 70% to the 1-cm crossing of resin at 532 nm. ie at the wavelength of the external excitation source.
- the DPA concentration was 0.22 mmol-L 1 , 27-fold lower than the concentration in Example No.1 and 27-fold higher than that of PtOEP.
- the photoinitiator, BAPO is able to initiate radical polymerization.
- This photoinitiator PI does not absorb light at the wavelength of the external excitation source (at 532 nm, included in the first wavelength range 520 nm at 550 nm), but absorbs in the spectral range 400 - 450 nm (second range of wavelengths) to absorb the secondary signal emitted by the annihilator.
- the concentration of PI was 32 mmol-L ⁇ in this example.
- the composition was bubbled through an inert gas, argon (Ar), prior to polymerization.
- argon Ar
- the composition was placed in a strip-culture chamber system (Lab-Tek TM) under a continuous argon stream to decrease the oxygen re-diffusion in the composition.
- the polymerization was carried out under micro-manufacturing conditions in an inverted microscope.
- the intensity of the external excitation source at 532 nm was 100 mW / cm 2
- composition according to the invention comprised:
- an acrylate-type monomer more specifically poly (ethylene glycol) diacrylate,
- PS photosensitizer a porphyrin, more specifically an octaethylporphyrin platinum, commonly known as PtOEP As annihilator AN, an anthracene derivative, more specifically a 9,10-diphenylanthracene, commonly abbreviated DPA, and
- phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide commonly abbreviated BAPO.
- the concentration of PtOEP was this time 7 ⁇ 1 , 20-fold lower than in Example No. 1.
- the transmission of the resin is 51% at the crossing of 1 cm of resin to the length of the 532 nm wavelength external excitation source included in this example in a first wavelength range of 520-550 nm.
- the concentration of DPA was 0.22 mmol-L 1 , 27-fold lower than the concentration in Example No. 1.
- the photoinitiator, BAPO does not absorb at the irradiation wavelength (532 nm), but absorbs in the spectral range 400-450 nm (second range of wavelengths in this example) to absorb the secondary signal emitted by the annihilator.
- the concentration of PI was 30 mmol-L ⁇ in the example.
- the resin was sparged with an inert gas, this time nitrogen (N 2 ), to decrease its oxygen content before polymerization. Then the tank was sealed to prevent the return of oxygen into the resin. The resin was exposed to an external irradiation source emitting at 532 nm with irradiance of about 50 mW-cnY 2 to initiate polymerization.
- the photosensitizer is chosen from photosensitizers having at least one of the following properties. The best results are obtained for photosensitizers having all the following properties.
- the photosensitizer PS must absorb the external excitation signal in order to make maximum use of the energy of the external light source emitted on the first wavelength range to generate the triplet states "1PS *". It must also be as transparent as possible to the light radiation (secondary signal) emitted by the annihilator over the second wavelength range so that the energy of the secondary signal is available to the photoinitiator.
- a photosensitizer PS comprising at least one molecule whose molar absorption coefficient on the first wavelength range is greater than at least two times, and preferably at least ten times, a coefficient of molar absorption of said molecule over the second wavelength range.
- the PtOEP thus absorbs ten times more the external excitation signal than the secondary signal emitted by the annihilator.
- a photosensitizer comprising a single molecule PtOEP was used.
- a photosensitizer comprising several types of photosensitizer molecules each photosensitizer molecule having, over at least a portion of the first wavelength range, a molar absorption coefficient greater than at least two time, and preferably at least ten times, the molar absorption coefficient of the same photosensitizer molecule over at least a portion of the second wavelength range.
- Molecules having similar absorption spectra are thus chosen, exhibiting a high absorption coefficient on adjacent parts of the first wavelength range, so that it is possible to illuminate the composition with a source of d excitation having a wider, more diffuse emission spectrum of the same limited power, while having a maximum of energy of the excitation signal absorbed by one or the other of the different molecules of the photosensitizer.
- a composition according to the invention is more or less liquid, more or less viscous or even solid and, to be used, it is stored in a tank of a shape suitable for the intended use or deposited on a substrate. In order for the composition to be polymerized to a thickness d, the external excitation signal must be able to penetrate the composition over the thickness d with sufficient energy.
- ⁇ is the molar extinction coefficient (also called molar absorptivity or molar absorption coefficient) of the photosensitizer
- d the thickness of the composition to be light cured.
- the optical system can also be immersed in the composition to be polymerized, liquid, to manufacture objects whose thickness is greater than d.
- the photosensitizer molecule must have a triplet state generation quantum yield greater than 0.1, and preferably greater than 0.5.
- that of PtOEP is 0.5 in polystyrene matrix and close to unity in solution.
- the photosensitizer molecule is chosen to have a lifetime in the triplet state greater than 10 ⁇ . This makes it possible to have effective energy transfer by diffusion and collision with the AN annihilator molecules.
- the triplet state PtOEP has a lifetime of 91 ⁇ en in polystyrene matrix and 50 ⁇ in a deoxygenated solvent.
- the photosensitizer PS molecule is chosen so that an energy level of the photosensitizer molecule in the triplet state "3PS *" is greater than an energy level of the molecule of the annihilator in the triplet state. 3 AM* "and so that an energy level of the photosensitizer molecule in the singlet state” 1PS * "is lower than an energy level of the molecule of the annihilator in the singlet state” 1 AM * ".
- This makes it possible to obtain efficient energy transfer from the triplet state "3PS *" to the triplet state "3 AM” and to limit or even prohibit a transfer of energy from the singlet state "1 AM". to the singlet state "1PS *".
- the photosensitizer molecules PS that may be used in the context of the invention, mention may be made in particular of:
- Metalloporphyrins for example an octaethyl-porphyrin platinium (PtOEP), an octaethyl-porphyrin palladium (PdOEP), a paladium-tetratolylporphyrin (PdTPP), a platinum (II) -tetraphenyltetrabenzoporphyrin (PtTPBP), or 9-paladium 10-dinaphthylanthracene (PdMeTPP), a paladium-meso-tetraphenyltetrabenzoporphyrin 1 (PdPh4TBP), a 1,4,8,11,15,18,22,25-octabutoxyphthalocyanine (PdPc (OBu) g),
- the molecules comprising an Ru (dmb) 3-, Ru-polypyridyl- radical, for example the Ru (dmb) 3-An molecule, with dmb a 4,4'-dimethyl, 2,2'-bipyridine and An of the anthracene,
- These molecules are likely to be excited, depending on the molecule, with a source emitting at a wavelength in the visible or near infrared. For example at wavelengths of 450 nm, 532 nm, 635 nm, 725 nm, depending on the molecules. Other molecules could be optimized for other wavelengths in near UV, visible or near infrared.
- the annihilator AN is chosen from annihilators having at least one of the following properties, the best results in the context of the invention being obtained for the annihilators having all the following properties.
- the annihilator AN must be as transparent as possible to the external excitation signal so that in no case the annihilator alone emits more than 10% of the photons, and preferably more than 1% of the photons, issued by the STTA-UC mechanism in the presence of the PS photosensitizer.
- the annihilator (AN) has a relative molar absorption coefficient over the first wavelength range less than 20%, and preferably less than 10%.
- a molar concentration of annihilator AN is greater than at least 10-fold and preferably at least 30-fold the molar concentration of the photosensitizer. This makes it possible to obtain a good energy transfer between the triplet state "3PS *" and the triplet state "3 AM”.
- the annihilator AN must have an emission quantum yield greater than 10% and preferably 50%.
- the DPA has a fluorescence yield of 0.9 in a cyclohexane solution.
- the molecule of annihilator AN is chosen to have a lifetime in the triplet state greater than 10 ⁇ . This makes it possible to have a collision probability between two molecules "3 AM” sufficient to have an effective annihilation between two molecules "3 AM” to obtain a molecule "1AM” in the singlet state excited to two photons.
- the molecule AN is chosen to have a singlet energy level "1 AM” less than twice its energy level in triplet state "3 AM". This facilitates the annihilation between two "3 AM” molecules to obtain a "1AM” molecule in the two-photon excited singlet state.
- an annihilator comprising a single molecule, for example DPA, was used.
- an annihilator comprising a plurality of molecules, a relative molar absorption coefficient of each molecule of the acceptor being less than 20% and preferably less than 10% over at least a part of the first range of wavelengths.
- the most transparent AM molecules are thus selected from the external excitation signal so that the energy transmitted by the external excitation signal is absorbed essentially by the photosensitizer and not by the annihilator.
- Using several AN annihilator molecules makes it possible to have a probability of collision between two molecules "3 AM” sufficient to have an effective triplet-triplet annihilation by diffusion and collision between two molecules "3 AM” to obtain a molecule "1 AM” in the singlet state excited at two photons.
- a derivative of anthracene for example anthracene (An), 9,10-diphenylanthracene (DPA), 9,10-dimethylanthracene (DMA), 9,10-dipolyanthracene (DTA), 2-chloro-9,10-diphtylanthracene (DTACI, 2-carbonitrile-9,10-dip-tolylanthracene (DTACN), 2-carbonitrile-9,10-dinaphthylanthracene (DNACN), 2-methyl- 9,10-dinaphthylanthracene (DNAME), 2-chloro-9,10-dinaphthylanthracene (DNACI), 9,10 bis (phenylethynyl) anthracene (BPEA), 2-chloro-9,10 bis (phenylethynyl) anthracene (2CB)
- a derivative of anthracene and a benzofuran derivative for example 1,3-diphenylisobenzofuran (DPBF)
- These molecules are capable of emitting a secondary signal whose emission peak is centered, according to the molecule, on the following wavelengths: 380-400 nm, 435-440 nm, 446-464 nm, 470-475 nm , 550-600 nm, ...
- a compound comprising a radical ruthenium (polypyridyl) 3- (Ru (dmb) 3), with a 4,4'-dmb dimethyl, 2,2'-bipyridine, such as the ruthenium compound (polypyridyl) 3- anthracene combined with 9,10-diphenylanthracene (DPA)
- DPA 9,10-diphenylanthracene
- PdPh 4 TBP a paladium-meso-tetraphenyltetrabenzoporphyrin 1 associated with 5,6,11,12- Tetraphenyl-naphthacene (rubrene)
- PdTAP paladium-raffantraporphyrin
- Rubrene 5,6,11,12-Tetraphenylnaphthacene
- PtOEP platinum octaethyl-porphyrin associated with 9,10-diphenylanthracene
- PdTPP palladium-meso-tetratolylporphyrin
- DPA 9,10-diphenylanthracene
- PdBrTPP palladium-tetrabromophenylporphyrin
- PdMeTPP palladium-tetramethylphenylporphyrin
- a 9,10-dinaphthylanthracene for example 2-carbonitrile-9,10-dinaphthylanthracene (DNACN), 2-methyl-9,10-dinaphthylanthracene (DNAMe) or 2- chloro-9,10-dinaphthylanthracene (DNACI)
- PtTPBP platinum (II) -tetraphenyltetrabenzoporphyrin (PtTPBP) associated with perylene, 9,10bis (phenylethynyl) anthracene (BPEA),
- the photosensitizer 1r (ppy) 3 is capable of efficiently absorbing a light signal having a wavelength in the first range 440 nm-460 nm (blue light signal), around the wavelength 450 nm which corresponds to an absorption peak for the compound Ir (ppy) 3.
- the pyrene, annihilator is capable of transmitting a light signal in the second range 380-400 nm (ultraviolet), around the wavelength 390 nm which corresponds to an emission peak for pyrene.
- the pair 1r (ppy) 3 / pyrene is capable of efficiently implementing an STTA-UC mechanism.
- the photosensitizer PdPc (OBu) 8 is capable of efficiently absorbing a light signal having a wavelength in the first range 710 nm-730 nm (red light), around the wavelength 725. nm which corresponds to an absorption peak for the compound PdPc (OBu) 8.
- the rubrene, annihilator, is able meanwhile to emit a light signal in the second range 550-600 nm (yellow light signal), around the wavelength 560 nm which corresponds to a peak emission for rubrene .
- the pair PdPc (OBu) 8 / rubrene is capable of efficiently implementing an STTA-UC mechanism.
- the first range and the second range of wavelengths can thus vary from one photosensitizer / annihilator couple to another, the essential point being, in the context of the invention, that the two ranges of wavelengths are distinct.
- the photoinitiator PI must not absorb the external excitation light signal so that more of the energy of this signal can be absorbed by the photosensitizer.
- the photoinitiator must best absorb the energy of the secondary signal emitted by the annihilator.
- the absorption spectrum of the photoinitiator must cover significantly (at least 80%) of the fluorescence emission spectrum of the annihilator in the singlet state. So in the examples described above, camphorquinone (CQ) and BAPO absorb well the secondary signal emitted by the annihilator over the 400-500 nm range.
- the photoinitiator must also be adapted to the resin to be polymerized.
- camphorquinone (CQ) and BAPO generate free radicals capable of initiating the polymerization of the selected acrylate resin, more specifically the pentaerythriol triacrylate or diacrylate of poly (ethylene glycol).
- CQ camphorquinone
- BAPO generate free radicals capable of initiating the polymerization of the selected acrylate resin, more specifically the pentaerythriol triacrylate or diacrylate of poly (ethylene glycol).
- other photoinitiators can be used, for example a photoinitiator capable of generating, depending on the case, acids or bases capable of initiating the ionic polymerization of certain resins.
- the photoinitiator may be associated with other co-initiator molecules, such as camphorquinone when combined with tertiary amines.
- the photoinitiator molecule is chosen to have a triplet state energy level " 3 PI *" higher than the energy level at the triplet state " 3 PS *” of the photosensitizer and at the level of triplet state energy " 3 AN *" of the annihilator. This makes it possible to avoid any unwanted reaction between the molecule " 3 PI *” and the molecule “ 3 PS *” or between the molecule " 3 PI *” and the molecule " 3 AN *".
- camphorquinone has a triplet energy level of the order of 2.2 eV, ie at least 0.3 eV more than the PtOEP (whose energy level at the triplet state is of the order of 1.9 eV) and that the DPA (whose energy level in the triplet state is of the order of 1.77 eV).
- the same molecule can be used for the annihilator and the photoinitiator.
- composition according to the invention are in particular:
- the reservoir containing the polymerizable resin is sealed or that the resin is polymerized under an inert atmosphere because of the diffusion of oxygen back.
- the first two methods consist of a step of removing the oxygen present in the composition, an initialization step carried out before a polymerization step of the composition.
- the third method consists in adding an antioxidant in the composition according to the invention.
- One or more types of antioxidant molecules that react with singlet oxygen resulting from the deactivation of triplet states of PS, AN and PI by molecular oxygen can be selected.
- the antioxidant molecule and its concentration are chosen so that singlet oxygen reacts preferentially with the antioxidant.
- the antioxidant reduces the concentration of singlet oxygen and therefore the dissolved molecular oxygen concentration in the resin also decreases.
- the oxygen concentration is sufficiently reduced so that its interaction with the triplet states of the components ( 3 PS *, 3 AN * and 3 PI *) is negligible, the STTA-UC phenomenon and the polymerization are triggered.
- the use of the antioxidant in the formulation induces a delay time (induction time) in the polymerization.
- Antioxidants can have several functions, more specifically they can be both antioxidants and annihilators, antioxidants and photoinitiators, antioxidants and photosensitizers or antioxidants and polymerizable monomers.
- the derivatives of anthracene, pyrene, rubrene may be used in the composition as annihilators and antioxidants at a time.
- the antioxidant is chosen to absorb at least 5 times less than the other compounds in the first and second wavelength ranges, with the exception of antioxidants that have multiple functions.
- the antioxidant is chosen such that its molar absorption coefficient is at least five times lower than the molar absorption coefficient of the photosensitizer (PS), the molar absorption coefficient of the annihilator (AN) and the molar photoinitiator (PI) absorption coefficient over the first wavelength range and the second wavelength range.
- the antioxidant is chosen so that it does not react with photosensitizers, annihilators and photoinitiators or with these components in their triplet or singlet states.
- the antioxidants that may be used in a composition according to the invention are in particular:
- Polycyclic aromatic hydrocarbon derivatives for example anthracene, pyrene, rubrene, naphthalene,
- Furan derivatives for example 2,5-dimethylfuran
- Unsaturated carboxylic acids for example oleic acid, Tertiary amines and their derivatives, for example N-methyldiethanolamine (MDEA) or triethylamine (TEA),
- MDEA N-methyldiethanolamine
- TAA triethylamine
- the resin used in the context of the invention may be any photopolymerizable resin, whatever the mechanism to implement to trigger the polymerization (radical mechanism, ionic mechanism, ).
- a photoinitiator appropriate to the mechanism to be used for initiating the polymerization and more specifically suitable for the resin to be polymerized will then be chosen, and then a photosensitizer / annihilator pair compatible with the photoinitiator and suitable for implementation of an STTA-UC mechanism.
- the resins that may be used include, for example:
- Monomers, oligomers or polymers radically polymerizable by addition or crosslinking mechanisms such as:
- acrylated monomers such as acrylates, polyacrylates, methacrylates, or
- acrylated oligomers such as unsaturated amides, or
- methacrylated polymers polymers which have a hydrocarbyl backbone and pendant peptide groups with a free radical polymerizable functionality, or
- vinyl compounds such as styrenes, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate, or
- Cationically polymerizable monomers and oligomers and cationically crosslinkable polymers for example epoxy resins such as monomeric epoxides and epoxy polymers having one or more epoxy groups, vinyl ethers, cyanate esters, etc. and mixtures of several of these compounds.
Abstract
Description
Claims
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FR1757401A FR3069862B1 (fr) | 2017-08-02 | 2017-08-02 | Composition photopolymerisable, materiau obtenu par polymerisation d'une telle composition et procede d'impression 3d utilisant une telle composition |
PCT/FR2018/051963 WO2019025717A1 (fr) | 2017-08-02 | 2018-07-31 | Composition photopolymérisable, matériau obtenu par polymérisation d'une telle composition et procédé d'impression 3d utilisant une telle composition |
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JP (1) | JP2021502466A (fr) |
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CN (1) | CN111164108A (fr) |
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US20220305724A1 (en) * | 2019-06-21 | 2022-09-29 | President And Fellows Of Harvard College | Triplet exciton acceptors for increasing upconversion thresholds for 3d printing |
WO2021154895A1 (fr) * | 2020-01-28 | 2021-08-05 | Quadratic 3D, Inc. | Impression tridimensionnelle (3d) comprenant une photopolymérisation par conversion ascendante |
EP3909748A1 (fr) | 2020-05-12 | 2021-11-17 | TIGER Coatings GmbH & Co. KG | Matériau thermodurcissant destiné à être utilisé dans une fabrication additive |
EP4161761A4 (fr) * | 2020-06-03 | 2023-11-22 | Quadratic 3D, Inc. | Procédés d'impression volumétrique en trois dimensions comprenant une feuille de lumière et systèmes |
FR3112345B1 (fr) | 2020-07-09 | 2023-04-21 | Univ Claude Bernard Lyon | Molécule amorceur pour une réaction d'absorption non linéaire, composition photopolymérisable activable par absorption biphotonique, et procédé d'impression 3D associé. |
FR3119562A1 (fr) | 2021-02-09 | 2022-08-12 | Universite Claude Bernard Lyon 1 | Procédé d'impression d'un objet à imprimer, et imprimante adaptée pour la mise en oeuvre du procédé. |
EP4094942A1 (fr) | 2021-05-26 | 2022-11-30 | TIGER Coatings GmbH & Co. KG | Composition durable par rayonnement pour une fabrication additive adaptée aux applications électroniques |
CN115873156B (zh) * | 2021-09-27 | 2023-12-15 | 四川大学 | 一种利用三线态-三线态湮灭上转换实现可见光光固化微纳3d打印的组合物 |
CN115028759A (zh) * | 2022-06-28 | 2022-09-09 | 华中科技大学 | 一种基于三线态上转换的激光制造方法及其应用 |
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FR2567668B1 (fr) * | 1984-07-16 | 1987-10-16 | Cilas Alcatel | Dispositif pour realiser un modele de piece industrielle |
JPH0586149A (ja) * | 1991-09-30 | 1993-04-06 | I C I Japan Kk | 光立体成形用樹脂組成物並びに立体成形体の形成方法 |
US6267913B1 (en) | 1996-11-12 | 2001-07-31 | California Institute Of Technology | Two-photon or higher-order absorbing optical materials and methods of use |
US7118845B2 (en) | 2000-06-15 | 2006-10-10 | 3M Innovative Properties Company | Multiphoton photochemical process and articles preparable thereby |
US20040198857A1 (en) | 2003-04-01 | 2004-10-07 | Dejneka Matthew J. | Photochemical reactions using multi-photon upconverting fluorescent inorganic materials |
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US20110021653A1 (en) | 2009-07-22 | 2011-01-27 | Lixin Zheng | Hydrogel compatible two-photon initiation system |
JP2014035527A (ja) * | 2012-08-10 | 2014-02-24 | Konica Minolta Inc | 有機感光体およびその製造方法 |
CN103483495B (zh) | 2013-09-16 | 2016-08-17 | 复旦大学 | 基于三线态-三线态湮灭上转换发光的光致形变高分子材料 |
JP2015122470A (ja) * | 2013-11-19 | 2015-07-02 | シャープ株式会社 | 液体アップコンヴァージョンマイクロカプセルの製造方法、液体アップコンヴァージョンマイクロカプセルを用いたアップコンヴァージョン層を有する太陽電池モジュールおよび表示装置 |
JP6255498B2 (ja) * | 2013-12-31 | 2017-12-27 | デンツプライ インターナショナル インコーポレーテッド | アップコンバージョン蛍光体を含有する歯科用組成物及び使用方法 |
EP3383969B1 (fr) * | 2015-12-02 | 2020-02-05 | Adolphe Merkle Institute, University of Fribourg | Matériaux polymères remplis de liquide à conversion optiquement ascendante |
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FR3069862A1 (fr) | 2019-02-08 |
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