EP4346744A1 - Composition polymérisable contenant un groupe thiol uréthane - Google Patents
Composition polymérisable contenant un groupe thiol uréthaneInfo
- Publication number
- EP4346744A1 EP4346744A1 EP22732030.6A EP22732030A EP4346744A1 EP 4346744 A1 EP4346744 A1 EP 4346744A1 EP 22732030 A EP22732030 A EP 22732030A EP 4346744 A1 EP4346744 A1 EP 4346744A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- weight
- urethane
- optionally
- formula
- 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 216
- 239000000178 monomer Substances 0.000 claims abstract description 107
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003999 initiator Substances 0.000 claims abstract description 40
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 150000005690 diesters Chemical class 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 125000000101 thioether group Chemical group 0.000 claims abstract description 23
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 18
- 150000005691 triesters Chemical class 0.000 claims abstract description 18
- 239000011256 inorganic filler Substances 0.000 claims abstract description 17
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 17
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001033 ether group Chemical group 0.000 claims abstract description 16
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- -1 alicyclic Hydrocarbon Chemical class 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims description 30
- 150000004706 metal oxides Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 125000002947 alkylene group Chemical group 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000005300 metallic glass Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011350 dental composite resin Substances 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 12
- 230000005855 radiation Effects 0.000 claims description 12
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 150000003568 thioethers Chemical class 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000002639 bone cement Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 210000000003 hoof Anatomy 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims description 4
- 239000005548 dental material Substances 0.000 claims description 3
- 238000005553 drilling Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000010146 3D printing Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003955 fissure sealant Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 24
- 239000002131 composite material Substances 0.000 description 17
- 150000003673 urethanes Chemical class 0.000 description 16
- 125000001931 aliphatic group Chemical group 0.000 description 14
- 150000003573 thiols Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 7
- 239000004971 Cross linker Substances 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical class CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 150000003254 radicals Chemical group 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical class CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 4
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000005368 silicate glass Substances 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- 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 3
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 3
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 2
- VCUNKEUDSCZBQQ-UHFFFAOYSA-N 2-[[3,3,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCC(C)CC(C)(C)CCNC(=O)OCCOC(=O)C(C)=C VCUNKEUDSCZBQQ-UHFFFAOYSA-N 0.000 description 2
- DNZPLHRZXUJATK-UHFFFAOYSA-N 2-sulfanylidene-5-[[5-[2-(trifluoromethyl)phenyl]furan-2-yl]methyl]-1,3-diazinane-4,6-dione Chemical compound FC(F)(F)C1=CC=CC=C1C(O1)=CC=C1CC1C(=O)NC(=S)NC1=O DNZPLHRZXUJATK-UHFFFAOYSA-N 0.000 description 2
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 2
- MENIJRPFVLNJIH-UHFFFAOYSA-N 5-benzyl-1,3-diazinane-2,4,6-trione Chemical class O=C1NC(=O)NC(=O)C1CC1=CC=CC=C1 MENIJRPFVLNJIH-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGOQVOGFDLVJAW-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O WGOQVOGFDLVJAW-UHFFFAOYSA-N 0.000 description 2
- APURLPHDHPNUFL-UHFFFAOYSA-M fluoroaluminum Chemical compound [Al]F APURLPHDHPNUFL-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- 125000002348 vinylic group Chemical group 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KCWWCWMGJOWTMY-UHFFFAOYSA-N 1-benzyl-5-phenyl-1,3-diazinane-2,4,6-trione Chemical compound O=C1C(C=2C=CC=CC=2)C(=O)NC(=O)N1CC1=CC=CC=C1 KCWWCWMGJOWTMY-UHFFFAOYSA-N 0.000 description 1
- CFKBCVIYTWDYRP-UHFFFAOYSA-N 10-phosphonooxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOP(O)(O)=O CFKBCVIYTWDYRP-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- SXEWOYJAMGWSMZ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCCOCCOCCO SXEWOYJAMGWSMZ-UHFFFAOYSA-N 0.000 description 1
- ALDLWNVQGSGVDF-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCCOCCOCCOCCO ALDLWNVQGSGVDF-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FHEPAJYPVFUTEE-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate;1-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]cyclohexane;oxepan-2-one Chemical compound OCCOC(=O)C=C.O=C1CCCCCO1.C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 FHEPAJYPVFUTEE-UHFFFAOYSA-N 0.000 description 1
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 1
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- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- RIYDTHLUCWFCEN-UHFFFAOYSA-N 5-benzyl-5-phenyl-1,3-diazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)C1(C=1C=CC=CC=1)CC1=CC=CC=C1 RIYDTHLUCWFCEN-UHFFFAOYSA-N 0.000 description 1
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- KYLIZBIRMBGUOP-UHFFFAOYSA-N Anetholtrithion Chemical group C1=CC(OC)=CC=C1C1=CC(=S)SS1 KYLIZBIRMBGUOP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- UUEYEUDSRFNIQJ-UHFFFAOYSA-N CCOC(N)=O.CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O Chemical compound CCOC(N)=O.CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O UUEYEUDSRFNIQJ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 description 1
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- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
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- 239000012963 UV stabilizer Substances 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- COHCXWLRUISKOO-UHFFFAOYSA-N [AlH3].[Ba] Chemical compound [AlH3].[Ba] COHCXWLRUISKOO-UHFFFAOYSA-N 0.000 description 1
- GXTNDOSGOPRCEO-UHFFFAOYSA-N [Cr].[Fe].[Zn] Chemical compound [Cr].[Fe].[Zn] GXTNDOSGOPRCEO-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- 230000002411 adverse Effects 0.000 description 1
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- KECAIQNCFZTEBM-UHFFFAOYSA-N antimony;chromium Chemical compound [Sb]#[Cr] KECAIQNCFZTEBM-UHFFFAOYSA-N 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- WAAOALIRKOAUMA-UHFFFAOYSA-N benzyl(dibutyl)azanium;chloride Chemical compound Cl.CCCCN(CCCC)CC1=CC=CC=C1 WAAOALIRKOAUMA-UHFFFAOYSA-N 0.000 description 1
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- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- REDWICFTZSAVSL-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O.CCOC(N)=O REDWICFTZSAVSL-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- WVLOSLDIIWIARX-UHFFFAOYSA-N hexadecane-7,7-diol Chemical compound CCCCCCCCCC(O)(O)CCCCCC WVLOSLDIIWIARX-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 229910052759 nickel Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- ZMASSMHNNATIBZ-UHFFFAOYSA-N prop-2-ynyl n-(3-triethoxysilylpropyl)carbamate Chemical compound CCO[Si](OCC)(OCC)CCCNC(=O)OCC#C ZMASSMHNNATIBZ-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052917 strontium silicate Inorganic materials 0.000 description 1
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003452 sulfinic acid derivatives Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052645 tectosilicate Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000006168 tricyclic group Chemical group 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
- A61K6/17—Particle size
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- 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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
- C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F290/147—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Definitions
- the invention relates to a polymerizable composition
- a polymerizable composition comprising 0.01 to 90% by weight of at least one inorganic filler component, 5 to 99.97% by weight comprising at least two urethane acrylates, with at least one urethane acrylate corresponding to formula I and the second urethane acrylate at least has a bifunctional thiolurethane group and at least one olefinic group and mixtures of urethane acrylates comprising these, 0.01 to 25% by weight of at least one di-, tri-, tetra- or multi-functional monomer having at least one ether group, thioether group, an at least tri-functional triester, in particular with thioether group(s), and/or a difunctional diester, the diester being selected from tricyclodecanedimethanol dimethacrylate and tricyclodecanedimethanol diacrylate or mixtures of these di-, tri-, tetra- or multifunctional monomers,
- the invention also relates to a polymerized composition with high flexural strength, high transparency and high double bond turnover and optionally low shrinkage in the production of three-dimensional articles or objects of greater than 5 mm in at least one of the three dimensions.
- the polymerized compositions exhibit low brittleness.
- a combination of bisphenol A glycidyl methacrylate (BisGMA) and triethylene glycol dimethacrylate (TEGDMA) as monomers for dental composites has established itself as one of the standards for dental composites in recent years. Due to the toxicity of the monomers, which has been proven in some cases, they should be substituted by non-toxic monomers with comparable physical properties, which is made possible by the monomer combinations used in this document.
- Urethane acrylates with bivalent aromatic groups are known from EP3135271B1. Polymerized compositions based on these urethanes exhibit good flexural strength and low shrinkage. The urethanes with aromatic groups tend to crystallize more than other urethanes.
- WO2019/107323 A1 discloses the production of thiols containing (meth)acrylate groups, such as thiocarbamates having at least one (met)acrylate group. Compositions based on these thiocarbamates have improved breaking strengths.
- EP3795597A1 discloses (meth)acrylate-functional thioethers with good breaking strength and toughness. The thioethers have lower viscosities than the thiocarbamates of WO2019/107323 A1.
- US2017/0007505A1 discloses diphenyl sulfide functional monomers and US10857073B2 discloses high refractive index difunctional phenyl sulfide monomers.
- EP3733150A1 discloses polyurethane resins in dental applications made from polythiols and polyisocyanates.
- US2007/0185230 A1 Oligomeric thio-ene systems from light-induced conversion of trithio/trivinyl which are said to have increased double bond conversion in dental compositions than dimethyl acrylate systems which have a double bond conversion of 55 to 75% and shrinkage that is too high.
- the thiol-ene monomers represent a monomer blend of thiol and acrylate, methacrylate or vinylic monomers.
- One disadvantage is the odor of these thiol-containing composites.
- the underlying polymerization mechanism in these monomer blends comprising thiol monomers and acrylate, methacrylate or vinylic monomers due to free radical chain transfer between thiol and (meth)acrylate is also significantly different from the free radical polymerization mechanism present in the compositions according to the invention.
- the technologies thus describe fundamentally different technologies.
- One object of the invention was to further improve the good mechanical properties of urethane acrylates. This should be done on the one hand by improving the storage stability of urethanes that tend to crystallize and, alternatively or additionally, by improving the transparency of the polymerized compositions. In addition, there was the object of increasing the conversion of double bonds in polymerizable compositions, preferably without adversely affecting the shrinkage of the composition. Furthermore, the mechanical properties of the polymerized compositions should advantageously be improved. Furthermore, one Improvement of the modulus of elasticity, especially in combination with an improved depth of hardening, may be possible.
- the invention relates to a polymerizable composition, in particular a dental composition, preferably a dental composite, comprising polymerizable urethane (alkyl) acrylates, in particular urethane (meth) acrylates, of the formula I and isomers of these and urethane (meth) acrylates comprising thiol (meth) acrylates, named below as urethane acrylates with a thiol group and an olefinic group, which are used as crosslinkers.
- the polymerizable composition also includes monomers that are referred to as so-called diluents. These monomers can include di- to multi-functional monomers with ether, thioether groups, triesters or diesters of tricyclodecane monomers. These monomers used as diluents are (meth)acrylate functional monomers.
- compositions comprising as a urethane acrylate a monomer 1, of formula I, and at least one further urethane acrylate referred to as monomer 2, in particular of the formulas V and VI with a thiolurethane group 2a, have very good depths of cure, flexural strength, modulus of elasticity and improved transparency and increased double bond conversion.
- Formula V with R 14 equal to Formula Vld with R 7 in which R 8 is -CH 2 -phenyl-CH 2 -, and R 10 equal to -CH(CH3)CH2- with R 15 equal to H.
- the urethane (meth)acrylate of the formula I and particularly preferably the monomer 1 shows very good properties in relation to the flexural strength, the modulus of elasticity (short E modulus) and the transparency.
- the monomers of the formula I can be prepared from corresponding diisocyanates with corresponding hydroxy-functional (meth)acylates or else diols with corresponding isocyanates; the preparation of monomer 1 is disclosed in EP 3135271 B1.
- a thiol of the formulas V or VI shows an increased tendency to crystallize. Surprisingly, this could be avoided by adding, in particular adding less than the stoichiometric amount, a thiol of the formulas V or VI.
- the preparation of the thiols is disclosed in WO2019/107323 A1. After addition of the thiol and the corresponding isocyanate, a thiol urethane (meth)acrylate, ie thiol ester, is formed with the following general structural formula V, which can be used as monomer 2a or 2 in component (ii) in the composition.
- R 14 can form different structures according to WO2019/107323 A1.
- the invention relates to a polymerizable composition comprising
- R 8 preferably comprises one of the following bivalent groups
- urethane acrylate in particular comprising urethane methacrylates and urethane acrylates, of the general formula V represents a urethane with an R 14 corresponding to the formula Vlb.
- the urethanes of the formula V can be prepared, for example, from the reaction of, for example, di- to polyfunctional thiols, such as thiol ethers or thiol esters of the exemplary structures 2b, 2c and 2d, with corresponding olefinic isocyanate groups
- the polymerizable compositions include urethane acrylates, the term urethane acrylates always also including urethane alkyl acrylates, such as urethane methacrylates, or a urethane acrylate without an alkyl group.
- acrylates are therefore combined to include acrylates and methacrylates, so when a chemical compound is referred to as acrylate in the present text, the term (meth)acrylates, which has been customary up to now, is always meant, which includes both methacrylates and acrylates.
- urethane acrylates corresponds to urethane (meth)acrylates), which always also include urethane methacrylates and urethane acrylates.
- urethane acrylates can also be described as urethane (meth)acrylates and acrylates as (meth)acrylates. The same applies to urethane (meth)acrylates (ii) containing thiolurethane groups.
- the invention also relates to a composition, in particular a dental composition, preferably a dental composite, in which the urethane acrylate of the general formula I and/or the formula V each independently with R 8 comprises bivalent aromatic hydrocarbon having 6 to 12 carbon atoms, bivalent alicyclic hydrocarbon having 6 to 12 carbon atoms or divalent linear or branched alkylene having 6 to 12 carbon atoms or divalent linear or branched alkylene with an aromatic or alicyclic group, in particular bi- or tricyclic group.
- a preferred mass ratio of the urethanes of the formulas I and V, in particular with formula(s) VI, is preferably 1:1 to 20:1, the mass ratio is preferably around 9:1, with the number 9 varying with plus/minus 1 can.
- the mass ratio of formulas I to V can be set as desired.
- a composition according to the invention comprises at least two urethane acrylates, in particular a mixture of at least these urethane acrylates, comprising at least one urethane acrylate of the formula I and the at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group, these Urethane acrylates are present in a mass ratio of from 1:1 to 100:1, in particular from 2:1 to 50:1, preferably from 5:1 to 20:1, more preferably from 7:1 to 10:1 ( ) : 1 +/- 1.
- the at least two urethane acrylates comprising at least one urethane acrylate of the formula I and at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group in a molar ratio of 1 to 2.5 to 0.0125 to 0.25, in particular from 0.5 to 1.25 to 0.0125 to 0.25.
- the two urethane acrylate monomers 1 and 2 preferably have an aromatic and rigid center in combination with flexible aliphatic structures in the periphery of the molecular structures, resulting in high mechanical strength of the thermoset polymer after radical polymerization of the monomer blend of 1 and 2, especially as Component (ii) of the polymerizable composition. Due to the spatial size and the flexible aliphatic side chains in the periphery of the molecular structures in 1 and 2, especially the prepolymer 2, there is a comparatively low polymerization shrinkage of the monomer blend from 1 and 2.
- the high proportion of sulfur atoms and the high aromatic content in the molecular structure of the monomer blends of 1 and 2 also leads to a high transparency of the composite, which in turn achieves a high depth of cure. In everyday clinical practice, high transparency is also desirable for the production of highly esthetic dental restorations. In addition, it was found that the use of the monomer blend from 1 and 2 leads to a comparatively high conversion of double bonds.
- a particularly preferred second urethane acrylate having at least one bifunctional thiolurethane group and having at least one olefinic group has a structure of the general formula V,
- R 13 is preferably the same as formula VIII
- R 7 equal to formula VII
- R 15 is H or C1 to C4 alkyl, preferably -CH3, with R 8 and R 10 as defined above and below. It is further preferred if the radical R 14 in formula V has one of the following structures Via to Vld
- each R 8 is independently a divalent hydrocarbon group having 6 to 12 carbon atoms
- each R 10 is independently selected from linear C2 to C6 alkylene groups or linear C2 to C6 oxyalkylene groups, where R 10 is optionally each independently has a C1-C3 alkyl group or (met)acryloxymethylene group, and with R 15 each independently being H, C1 to C4-alkyl, in particular CH 3 or H.
- R 5 and R 6 are each independently selected from C2 to C6 linear alkylene groups or C2 to C6 linear oxyalkylene groups, with R 5 and R 6 optionally each independently being a C1-C3 alkyl group or (met)acryloxymethylene group. Therefore, R 5 , R 6 or even R 10 can each independently comprise: C2-6 alkylene group in which a hydrogen atom can be substituted with a C1-3 alkyl group or a (meth)acryloyloxymethylene group, or a linear one Oxyalkylene group containing a hydrogen atom with a C1-3 alkyl group or a (meth)acryloyloxymethylene group can be substituted.
- the aforementioned alkyl groups are preferably linear.
- linear alkylene groups examples include -CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- , -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, with preferred ones -CH2CH2- , -CH2CH2CH2- , -CH2CH2CH2CH2- .
- _ _ _ Preferred linear oxyalkylene groups include -CH2CH2OCH2CH2- and -CH2CH2OCH2CH2OCH2CH2-, with CH2CH2OCH2CH2- being preferred.
- the aforementioned groups can each have a hydrogen atom substituted by a methyl group or (meth)acryloxy group.
- Preferred urethanes of the general formula I include the urethanes of the formulas Ia
- R 11 is each independently H, C1-C3 alkyl groups or (met)acryloxymethylene group, preferably H or CH 3 . Both R 11 can be the same or different. With R 8 as defined above as specific groups.
- the two urethane acrylate monomers and optionally further urethane acrylates require the addition of a reactive diluent due to the comparatively high viscosity of monomers 1 and 2 in order to adjust the processability of the composition, in particular as a dental composite.
- Component (iii) preferably has the at least one di-, tri-, tetra- or multifunctional monomer having at least one ether group, thioether group, an at least trifunctional triester and/or a difunctional diester, the diester is selected from tricyclodecanedimethanol dimethacrylate and tricyclodecanedimethanol diacrylate or mixtures comprising at least two of these di-, tri-, tetra- or multifunctional monomers a viscosity of less than or equal to 2000 mPas, preferably less than or equal to 1000 mPas, particularly preferably less than or equal to 500 mPas .
- the aforementioned monomers of component (iii) are preferably aliphatic and/or cycloaliphatic bis(meth)acrylates with a viscosity of less than or equal to 2000 mPas, preferably less than or equal to 1000 mPas, particularly preferably less than or equal to 500 mPas.
- component (iii) monomers which can be used in combination with the urethanes of component (ii) include, preferably, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol dimethacrylate, tricyclodecanedimethanol diacrylate.
- acrylate-functional thioethers or tri- or tetra-functional esters can be used as component (iii).
- a combination with thioethers as component (iii) has particularly high transparency combined with low shrinkage and high double bond conversion. These properties are particularly advantageous in dental applications for the production of dental composites.
- Each of the monomers of components (iii) advantageously has a viscosity of less than or equal to 2000 mPas, preferably less than or equal to 1000 mPas, particularly preferably less than or equal to 500 mPas.
- Preferred di-, tri-, tetra- or multi-functional monomers having at least one thioether group, preferably as reactive diluents are di- to multi-functional thio(meth)acrylate compounds. These are thioacrylates and thio(meth)acrylates, which are distinguished by the absence of aromatic groups such as phenyl, phenylene or bisphenol-A in the molecular structure.
- thioacrylates and thio(meth)acrylates which are distinguished by the absence of aromatic groups such as phenyl, phenylene or bisphenol-A in the molecular structure.
- the preparation of acrylates containing thioether groups is disclosed in EP3795597A1, to which reference is made in its entirety.
- the monomers in component (iii) comprising thioether groups can in particular comprise at least one of the following monomers or also mixtures of at least two of the monomers of component (ii). Particular preference is given to using one or more of the following monomers 4 to 9 in component (iii).
- the thioether group-containing monomers in particular the thio(meth)acrylates
- there is also increased transparency of the resulting composite comprising at least two urethanes - monomers 1 and 2 and the Monomers of component (iii), in particular the respective reactive diluents 4 to 9 achieved.
- the reactive diluents 4 to 9 as component (iii) have a high molecular weight compared to commercially available reactive diluents, which leads to comparatively low polymerization shrinkage.
- the comparatively high molecular weight of the reactive diluents 4 to 9 leads to a lower brittleness of the polymerized composite, which can be determined from the relationship between the modulus of elasticity and the flexural strength, as can be seen, for example, from the exemplary embodiments.
- the monomers of component (ii), in particular the reactive diluents containing thioether groups or tri- or tetra-ester groups, can be used in combination with the monomer blend of 1 and 2, of the formulas I and V, either individually or in mixtures with one another.
- the polymerizable composition particularly preferably comprises as component (iii) at least one di-, tri-, tetra- or multifunctional monomer having at least one ether group of the formula III, thioether group of the formula IV and/or an at least tri- or tetrafunctional triester of the formula II or mixtures of at least two of the monomers, in particular comprising at least one monomer of the formulas IIa, Mb, IIc, III, IVa, IVb, IVc and/or IVd
- compositions comprise: (i) 5 to 40%, especially 5 to 30% by weight of an inorganic
- Filler component in particular comprising at least one glass, in particular dental glass, silicate, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, zinc oxide and/or mixtures of at least two of the components mentioned, the components have an average particle size of 0.2 mhi to 10 mhi, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, and
- urethane acrylates comprising at least one urethane acrylate of the formula I and at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group
- compositions include:
- an inorganic filler component in particular comprising at least one glass, in particular dental glass, silicate, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide, zinc oxide and/or mixtures of at least two of the components mentioned, the components having an average particle size of 0.2 mhi to 10 mhi, and optionally at least one amorphous metal oxide having an average primary particle size of 10 nm to 115 nm, and
- urethane acrylates comprising at least one urethane acrylate of formula I and at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group.
- composition of the composition being 100% by weight.
- An equally particularly preferred composition comprises
- an inorganic filler component in particular comprising at least one glass, in particular dental glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and/or zinc oxide with an average particle size of 0.4 ⁇ M to 10 mhi, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, and
- urethane acrylates comprising at least one urethane acrylate of the formula I and at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group, or a mixture of urethane acrylates of the formulas I and V and optionally of isomers of the formula I,
- compositions include:
- an inorganic filler component in particular comprising at least one glass, in particular dental glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide and/or zinc oxide with an average particle size of from 0.4 mgH 10 mhi, and optionally at least one amorphous metal oxide with an average primary particle size of 10 nm to 115 nm, and
- compositions include
- urethane acrylates comprising at least one urethane acrylate of the formula I and at least one second urethane acrylate having at least one bifunctional thiolurethane group and at least one olefinic group, or a mixture of urethane acrylates of the formulas I and V and optionally of isomers of the formula I,
- urethanes include urethanes of the formula I and optionally of the formula V with VII and/or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R 1 , R 2 and R 15 each independently selected from H and alkyl with 1 to 8 carbon atoms, R 1 , R 2 and R 15 are particularly preferably H or CH 3 .
- Particularly preferred urethane acrylates of the formula I or mixtures of urethane acrylates include urethanes of the formula I and optionally mixtures of isomers with R 1 , R 2 , R 8 and R 11 as defined above,
- Urethane acrylates of the formula I very particularly preferably include at least one compound of the formulas Ic to Io and/or mixtures of these and optionally mixtures of isomers of these, and/or mixtures of these urethanes of the formula I and optionally mixtures of the isomers of the aforementioned compounds with R 1 and R 2 each independently selected from H and alkyl having 1 to 8 carbon atoms, le
- compositions with (iii) 0.01 to 15% by weight of at least one di-, tri-, tetra- or multi-functional monomer are also preferred, the total composition of the composition being 100% by weight.
- the compositions can comprise at least one inorganic filler component comprising at least one glass, silicate, feldspar, Metal oxide Mixed oxide, silicon dioxide, zirconium dioxide with an average particle size dso of 0.5 to 10 mGP.
- compositions comprising a) at least one inorganic filler component comprising at least one glass, silicate, quartz, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide or a mixture comprising at least two of the components with an average particle size of dso of 1.8 mhi, and preferably dg9 less than or equal to 20 mhi, or b) at least one inorganic filler component comprising at least one glass, feldspar, metal oxide, mixed oxide, silicon dioxide, zirconium dioxide or a mixture comprising at least two of the components as a mixture of different fractions with mean particle sizes, with i) dso from 2 to 8 mhi, ii) dso from 1.0 to 2.0 mhi, and iii) dso from 0.5 mhi to 2 mhi, the fractions of i) to ii) to iii) in the ratio of 1 to 4:1:4 to 8, especially from 2 to
- compositions can comprise as amorphous metal oxide at least one non-agglomerated amorphous metal oxide with a primary particle size of 2 to 150 nm, and wherein the amorphous metal oxide optionally comprises precipitated silica, fumed silica, zirconia or mixed oxides.
- compositions particularly preferably comprise as (i) inorganic filler component (i.1) 0.005 to 85% by weight, in particular 50 to 85% by weight, of at least one glass, silicate, quartz, feldspar, metal oxide mixed oxide, silicon dioxide, zirconium dioxide or a mixture comprising at least two of these filler components, and optionally (i.2) 0.005 to 5% by weight, in particular 0.05 to 2% by weight, amorphous metal oxide, in particular fumed silica and/or precipitated silicon dioxide, in particular 0 1 to 90% by weight, in particular 50.005 to 90% by weight, of filler component, based on the total composition of the composition of 100% by weight.
- compositions may comprise as (iii) monomers selected from di-methacrylic esters of polyethers, tri-, tetra- or multi-functional methacrylic esters of polyethers and 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy- propoxy)phenyl]propane, bis(2'-oxa-3'-oxopentyl-4'-ene)tetrahydrodicyclopentadiene, triesters of thioethers, diesters including tricyclodecane, and isomers thereof and optionally pentaerythritol tetrapropoxyacrylate.
- monomers selected from di-methacrylic esters of polyethers, tri-, tetra- or multi-functional methacrylic esters of polyethers and 2,2-bis-[4-(2-hydroxy-3-methacryloyloxy- propoxy)phenyl]propane, bis(2'-oxa-3'-oxopenty
- Component (iii) may preferably include dimethacrylate polyethylene glycol, dimethacrylate polypropylene glycol. Especially preferred are dimethacrylate triethylene glycol (TEGDMA), diethylene glycol dimethacrylate (DEGMA) and dimethacrylate tetraethylene glycol (TEDMA).
- TEGDMA dimethacrylate triethylene glycol
- DEGMA diethylene glycol dimethacrylate
- TEDMA dimethacrylate tetraethylene glycol
- a composition may comprise as (v) from 0.01% to 15% by weight of a polymeric particulate filler, the total composition of the composition being 100% by weight.
- Preferred stabilizers include water, at least one benzophenone and/or at least one phenol derivative.
- the invention also relates to polymerized compositions, in particular obtained or obtainable by polymerization of one of the polymerizable compositions, the polymerized compositions comprising
- At least one polymer, in particular copolymer based on the polymerization of at least monomers and/or prepolymers comprising at least two urethane acrylates, where at least one urethane acrylate of the formula I, as defined above and below, with a bivalent hydrocarbon group and the second urethane acrylate has at least one bifunctional thiol urethane group and at least one olefinic group, and/or mixtures of urethane acrylates comprising these, and
- the diester is selected from tricyclodecanedimethanol dimethacrylate and tricyclodecanedimethanol diacrylate or mixtures of at least two of the di-, tri-, tetra- or multifunctional monomers, and - 0 to 10% by weight, in particular 0.01 to 10% by weight, preferably 0.01 to 10 % by weight of at least one pigment, the total composition of the polymerized composition being 100% by weight.
- the invention also relates to a polymerized composition obtained or obtainable by polymerizing the composition i) with a UV and/or Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to 530 nm, preferably with at least one Maximum or maxima in the spectral range from 400 to 500 nm and / or thermal polymerization ii). a pressure of 50 to 300 MPa and/or elevated temperature, preferably at 90 to 150°C.
- the polymerized composition is preferably in the form of a block of material, in particular the block of material is in the form of a three-dimensional geometric shaped body, in particular as a milling blank without an adapter or as a milling blank with an adapter for fixing in an automated material-removing device.
- the composition is very particularly preferred for use as a dental material, in particular as a fissure sealant, dental composite material, direct adhesive dental restoration, as a hoof repair material, as a bone cement, or as a bone cement for cementing artificial joint prostheses.
- the invention also relates to the use of a polymerizable composition, in particular as a dental composite material, preferably in additive manufacturing processes, in radiation-based generative manufacturing processes, in a stereolithography process, SLA process (laser-based stereolithography process), a DLP process (digital light Processing) or an SLA and DLP process, in generative LED beamer-based manufacturing processes, in radiation and thermal-based generative manufacturing processes, in thermal generative manufacturing processes, in 3D printing processes, multitjet processes (MJM) or polyjet processes, and /or b) for the production of dental prosthetic supplies, orthodontic appliances and/or instruments in a material-removing process, in particular in a process in which the polymerized composition is removed by means of milling, cutting, polishing, breaking, chipping and/or drilling, in particular e in a process in which the polymerized composition is ablated using laser energy.
- a polymerizable composition in particular as a dental composite material, preferably in additive manufacturing processes, in radiation-based generative manufacturing processes,
- the invention also relates to the use of a polymerizable composition in radiation-based polymerization processes, in particular UV and/or VIS polymerization processes, free-radically induced polymerization processes, thermally based polymerization processes and/or redox-based polymerization processes.
- radiation-based polymerization processes in particular UV and/or VIS polymerization processes, free-radically induced polymerization processes, thermally based polymerization processes and/or redox-based polymerization processes.
- the invention relates to the use of a polymerizable or a polymerized composition for the production of dental prosthetics Provisions including crowns, inlays, onlays, superstructures, artificial teeth, dental bridges, dental bars, spacers, abutments, veneers or for the production of a bite splint, milling blank, dental prosthesis, part of a surgical prosthesis, drilling template, implant, mouthguard, joint prosthesis, telescope, implant part, orthodontic appliance, instrument or hoof part.
- component (iii) comprising at least one of the monomers 4 to 9
- triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol dimethacrylate, tricyclodecanedimethanol diacrylate or mixtures of at least two All commercially available photoinitiators can be used for the monomers.
- a combination of camphorquinone with 2-ethylhexyl-4-dimethylaminobenzoate (EHA) is preferably used in the composition.
- peroxides or hydroperoxides for example, and redox initiators for auto- or cold-polymerization can be used for thermal polymerization.
- redox initiators for auto- or cold-polymerization
- the composition is formulated as a 2K composition that polymerizes only after the two components have been mixed.
- a thermally polymerizable composition is understood here to mean a composition which can be polymerized at greater than or equal to 60 to 150.degree. C., preferably at greater than or equal to 70 to 150.degree. C., particularly preferably from 90 to 150.degree. It is further preferred according to the invention if the volume shrinkage is small.
- the invention also relates to a dental composite material obtainable by polymerization i) with a UV/Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range from 400 to 500 nm and optionally ii) at a pressure of 50 to 300 MPa and/or elevated temperature, preferably at 90 to 150° C., or i) with a UV and/or Vis radiation source, preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to 530 nm, preferably with at least one maximum or maxima in the spectral range from 400 to 500 nm and/or ii) at a pressure of 50 to 300 MPa and/or elevated temperature, preferably at 90 to 150°C.
- a UV/Vis radiation source preferably with a Vis radiation source with emission maxima in the spectral range from 380 nm to
- the polymerizable compositions can also contain other additives, such as stabilizers, colorants and pigments, microbiocidal active ingredients, fluoride ion-releasing additives, optical brighteners, plasticizers and/or UV absorbers, inhibitors and UV stabilizers.
- additives such as stabilizers, colorants and pigments, microbiocidal active ingredients, fluoride ion-releasing additives, optical brighteners, plasticizers and/or UV absorbers, inhibitors and UV stabilizers.
- Glasses are preferably: aluminum silicate glasses or fluoroaluminum silicate glasses, fluoroaluminum silicate glasses containing boron, barium aluminum silicate, strontium silicate, strontium borosilicate, potassium silicate, calcium borosilicate, sodium silicate glass, potassium silicate glass, lithium silicate and/or lithium aluminum silicate and mixtures of at least two of the aforementioned glasses.
- Amorphous spherical fillers based on oxide or mixed oxides, such as amorphous S1O2, ZrO2 or mixed oxides of S1O2 and ZrO2, can be used as amorphous metal oxide or as a mixture of amorphous metal oxides.
- mixed oxides of zirconium dioxide and silicon dioxide, zirconium dioxide or zinc oxide as well as crystalline silicates can be used as filler components in the composition.
- All fillers, such as glasses, amorphous metal oxides or radiopaque and/or pigments are preferably functionally silanized.
- Suitable silanes are, in particular, thiol-, vinyl-, allyl-, norborn-2-enyl-, methacrylic- or alkyne-functionalized silanes.
- the invention thus also relates to compositions comprising fillers functionally silanized with thiol-, vinyl-, allyl-, norborn-2-enyl-, methacryl- or alkyne-functionalized silanes.
- the amorphous metal oxide is preferably a non-agglomerated amorphous metal oxide with a primary particle size of 2 to 150 nm, in particular 2 to 100 nm, preferably 2 to 45 nm, the amorphous metal oxide being silicon dioxide, precipitated silicon dioxide, fumed silica, zirconium oxide, mixed oxides or mixtures this includes, in particular, the metal oxides are silanized.
- (Meth)acryloxyalkyl-functional silanes or other alkyl- or olefinically-functionalized silanes can be considered as silanizing agents.
- fillers can be added to the compositions for the production of dental composites.
- Fillers based on oxides with a particle size of 0.4 ⁇ m to 20 ⁇ m such as S1O2, ZrO2 and T1O2 or mixed oxides of S1O2, ZrO2, ZnO and/or T1O2 are particularly suitable.
- nanoscale or microfine fillers with a particle size of 0.01 to 500 nm are used, such as pyrogenic ones silicic acid or precipitated silicic acid.
- fillers dental glasses and / or tectosilicates with a particle size of 0.4 pm to 20 pm and / or 0.01 mm to 15 mm such as quartz powder, glass ceramic powder and / or feldspar powder or X-ray opaque dental glass powder of barium or strontium aluminum silicate glasses, and radiopaque fillers with a particle size of 0.4 ⁇ m to 20 ⁇ m and/or 0.01 mm to 15 mm are used.
- This can also be ytterbium trifluoride, tantalum(V) oxide, barium sulfate or mixed oxides of S1O2 with ytterbium(III) oxide or tantalum(V) oxide, in particular of the aforementioned particle sizes of 0.4 ⁇ m to 20 ⁇ m and/or 0.01 mm up to 15 mm can be used. All particle sizes mentioned are weight-average particle sizes, such as D50 in particular.
- Si0 2 -based fillers can be surface-modified with thiol-, vinyl-, allyl-, norborn-2-enyl-, methacryl- or alkyne-functionalized silanes.
- silanes are 3-thiopropyltrimethoxysilane, 3-allyltriethoxysilane, methacryloxypropyltrimethoxysilane or N-[3-(triethoxysilyl)propyl]carbamic acid propargyl ester.
- Functionalized acid phosphates such as 10-methacryloyloxydecyl dihydrogen phosphate can also be used to modify the surface of non-siliceous fillers such as ZrÜ2 or PO2.
- the composition may contain a polymeric particulate filler content in addition to the inorganic filler component.
- the total content of such a polymeric particulate filler can be from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight in the total composition of the composition of 100% by weight.
- the particle sizes of the polymeric filler are preferably in the range from 10 to 200 microns, in particular from 30 to 90 microns, particularly preferably 20 to 50 microns.
- acrylate in the present invention includes (alkyl) acrylate or (meth) acrylate or urethane (alkyl) acrylate with (alkyl) in brackets or urethane (meth) acrylate with (meth) in brackets means that the term acrylates or urethane acrylates with and without alkyl groups or methyl group.
- the alkyl groups preferably contain 1 to 10 carbon atoms, preferably 1 to 2 carbon atoms, in the urethane alkyl acrylates mentioned.
- the alkyl groups preferably contain 1 to 10 carbon atoms, preferably 1 to 2 carbon atoms, in the (alkyl)acrylates mentioned.
- Component (ii) comprising at least two urethane acrylates can additionally comprise at least one difunctional urethane acrylate, urethane (alkyl) acrylate, urethane (alkyl) acrylate with divalent alkylene group or urethane (meth) acrylate with divalent alkylene group, this is preferably selected from linear or branched urethane dimethacrylates functionalized with a bivalent alkylene group, urethane dimethacrylate-functionalized polyethers with alkylene group(s), such as bis(methacryloxy-2-ethoxycarbonylamino)-alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyalkylene ethers, preferably 1 ,6-Bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane, UDMA alternatively named HEMA-TDMI.
- a bis(methacryloxy-2-ethoxycarbonylamino)-alkylene is preferred, where alkylene comprises linear or branched C3 to C20, preferably C3 to C6, such as particularly preferably an alkylene substituted with methyl groups, such as HEMA-TMDI.
- the divalent alkylene preferably includes 2,2,4-trimethylhexamethylene and/or 2,4,4-trimethylhexamethylene.
- the component (ii) may include di-HEMA trimethylhexyl dicarbamate, diurethane dimethacrylate, a methacrylate adduct, urethane dimethacrylate.
- R'CH2[C(CH3)(R)CH2]2CH2 R ', R H or CH3
- the composition can be added to the composition as a stabilizer to improve consistency and flow behavior for process engineering workability.
- Stabilizers are preferably added to the composition to prevent premature polymerisation and to give the material a certain shelf life.
- the composition comprises in component (iv) at least one stabilizer selected from water, at least one benzophenone derivative, preferably alkoxy-substituted benzophenone and/or phenol derivative, such as 2-hydroxy-4-methoxybenzophenone, 2,6-bis (1,1-dimethyl)-4-methylphenol, or a mixture of the three stabilizers.
- the stabilizers are preferably present at 0.01 to 10% by weight in the total composition, particularly preferably from 0.7 to 10% by weight, in particular from 0.5 to 2% by weight. Furthermore, it is preferred if the composition contains 0.01 to 2% by weight of water as a stabilizer, preferably 0.1 to 1.0% by weight of water.
- At least one pigment comprising at least one fluorescent pigment and optionally at least one organic color pigment and/or at least one inorganic color pigment such as titanium dioxide, in particular non-fluorescent color pigments, can be added to optimally adjust the color and the aesthetics of the polymerized composition.
- the at least one fluorescent pigment is preferably an organic one Fluorescent pigment, in particular a non-polymerizable organic fluorescent pigment optionally comprising aryl carboxylic acid esters, aryl carboxylic acids, coumarin, rhodamine, naphthanic imide or a derivative of the respective substance.
- Inorganic fluorescent pigments may include CaAI 4 O 7 :Mn 2+ , (Ba0.98Eu0.02)MgAlioOi 7 , BaMgF 4 :Eu 2+ , Y(1 995)Ce(0.005)SiO 5 .
- the composition can comprise organic pigments and also inorganic pigments, in particular comprising diethyl 2,5-dihydroxyterephthalate, N,N'-bis(3,5-xylyl)perylene-3,4:9,10-bis (dicarbimide), copper phthalocyanine, titanate pigment, in particular chromium antimony titanate (rutile structure), spinel black, in particular pigments based on iron oxide black (Fe 3 0 4 ), iron (Fe) being partially substituted by chromium and copper or nickel and chromium or manganese , zinc iron chromium spinel, brown spinel, ((Zn,Fe)(Fe,Cr) 2 0 4 ) cobalt zinc aluminate blue spinel and/or titanium oxide.
- the pigments, including fluorescent and color pigments are preferably present in the total composition at 0.01 to 10% by weight, particularly preferably from 0.01 to 5% by weight, preferably from 0.01 to 1%
- the composition may comprise: (iv) 0.01 to 2% by weight of a UV and/or Vis photoinitiator or a UV and/or Vis photoinitiator system, and 0.01 to 2 wt% stabilizer.
- the polymerized composition can be used to produce technical components that are particularly exposed to high mechanical loads, such as plastic templates, nails, screws and other components familiar to the person skilled in the art, etc.
- urethane (meth)acrylates of component (ii) at least one urethane (meth)acrylate, in particular a urethane dimethacrylate, preferably a bis(methacryloxy-2-ethoxycarbonylamino)alkylene, diurethane acrylate oligomers, alkyl functional urethane dimethacrylate oligomers, aromatically functionalized urethane dimethacrylate oligomers, aliphatic unsaturated urethane acrylates, bis(methacryloxy-2-ethoxycarbonylamino) substituted polyethers, aromatic urethane diacrylate oligomers, aliphatic urethane diacrylate oligomers, aliphatic urethane diacrylates, hexafunctional aliphatic urethane resins, aliphatic urethane triacrylate, aliphatic Urethane acrylate oligomer, unsaturated ali
- difunctional and polyfunctional urethane (meth)acrylates such as in particular urethane di(eth)acrylates, particular preference being given to at least one (iii) urethane dimethacrylate selected from linear or branched alkyl-functionalized urethane dimethacrylates, urethane dimethacrylate-functionalized polyethers, in particular bis(methacryloxy-2- ethoxycarbonylamino)-alkylene, bis(methacryloxy-2-ethoxycarbonylamino)-substituted polyethers, preferably 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane.
- urethane dimethacrylate selected from linear or branched alkyl-functionalized urethane dimethacrylates
- urethane dimethacrylate-functionalized polyethers in particular bis(methacryloxy-2- ethoxycarbonylamino)-alkylene, bis
- Suitable urethane (meth)acrylates are available under the following trade names: Ebecryl 230 (aliphatic urethane diacrylate), Actilane 9290, Craynor 9200 (di-urethane acrylate oligomer), Ebecryl 210 (aromatic urethane diacrylate oligomer), Ebecryl 270 (aliphatic urethane diacrylate oligomer), Actilane 165, Actilane 250, Genomer 1122 (monofunctional urethane acrylate), Photomer 6210 (Cas No.
- the urethane (meth)acrylates can preferably be selected from the aforementioned urethane (meth)acrylates or from a mixture of at least two different, preferably at least three different, aforementioned urethane (meth)acrylates.
- the at least one di-, tri-, tetra- or multi-functional monomer of component (iii) can also comprise at least one of the following monomers, in particular a mixture of monomers comprising bis-(2'-oxa-3'-oxo- pentyl-4'-en)tetrahydrodicyclopentadiene and isomers thereof, 1,4-butanediol dimethacrylate (1,4-BDMA) or pentaerythritol tetraacrylate, decanediol di(meth)acrylate, dodecanediol di(meth)acrylate, hexyldecanediol di(meth )acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and butanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, a mixture containing at least
- At least one of the following monomers can be present in the composition comprising at least one monomer, in particular a mixture of monomers of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, n-hexyl methacrylate, 2 -phenoxyethyl methacrylate, isobornyl methacrylate, isodecyl methacrylate, Polypropylene glycol mono-methacrylate, tetrahydrofuryl methacrylate, methyl acrylate,
- the invention also relates to a composition which preferably additionally contains at least one or more substance(s) from the groups of fillers, pigments, stabilizers, regulators, antimicrobial additives, UV absorbers, thixotropic agents, catalysts and crosslinkers.
- additives - like pigments, stabilizers and regulators - are used in rather small amounts, e.g. B. a total of 0.01 to 3.0, especially 0.01 to 1.0 wt .-% based on the total composition of the composition.
- Suitable stabilizers are e.g. B. hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol (BHT).
- the composition preferably contains from 0.01 to 10% by weight, in particular from 0.5 to 5% by weight, preferably 0.5 to 2% by weight, of at least one initiator or initiator system, preferably i) at least one photoinitiator for the UV and/or Vis range or a photoinitiator system for the UV and/or Vis range and optionally at least one stabilizer, and optionally further customary additives, optionally pigment(s) or dye(s).
- photoinitiators include alpha-hydroxyphenyl ketone, benzildimethylketal or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid ethyl ester, and mixtures of at least two of the photoinitiators bisacylphosphine oxides (BAPO). Or also camphorquinone with amines selected from N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and diethyl p-dimethylaminobenzoate.
- BAPO bisacylphosphine oxides
- Typical stabilizers include 2,6-di-tert-butyl-4-methylphenol (BHT) or hydroquinone monomethyl ether (MEHQ), 2-hydroxy-4-methoxybenzophenone, HALS (Hindered Amine Light Stabilizers), benzotriazole ultraviolet absorbers (UVAs), and hydroxy Phenyl triazines (HPT).
- BHT hydroquinone monomethyl ether or 2,6-di-tert-butyl-4-methylphenol
- Peroxides, hydroxyperoxides, optionally azo compounds, or mixtures comprising these are suitable as initiators, in particular thermal initiators or initiator systems.
- Suitable thermal initiators can be used as free-radical initiators in the temperature range from 70 to 150.degree. C., preferably from 90 to 150.degree.
- Preferred thermal initiators include at least one initiator selected from: dilauroyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, 2,2'-azobis-isobutyronitrile, benzylbarbituric acid derivative, particularly preferably tert-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, dicumyl peroxide, dicumyl hydroperoxide, azobisisobutyronitrile, benzylbarbituric acid derivatives such as phenylbenzylbarbituric acid, cyclohexylbenzylbarbituric acid.
- the following initiators and/or initiator systems for auto- or cold-polymerization include a) at least one initiator, in particular at least one peroxide and/or azo compound, in particular LPO: dilauroyl peroxide, BPO: dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis-(isobutyronitrile), DTBP: di-tert-butyl peroxide, and optionally b) at least one activator, in particular at least one aromatic amine, such as N,N-dimethyl-p-toluidine, N,N -Dihydroxyethyl-p-toluidine and/or diethyl p-dibenzylaminobenzoate or c) at least one initiator system selected from redox systems, in particular a combination selected from dibenzoyl peroxide, dilauroyl peroxide and
- the initiator system can be a redox system comprising a peroxide and a reducing agent selected from ascorbic acid, ascorbic acid derivative, barbituric acid or a barbituric acid derivative, sulfinic acid, sulfinic acid derivative, a redox system comprising (i) barbituric acid or thiobarbituric acid or a barbituric acid is particularly preferred or thiobarbituric acid derivative and (ii) at least one copper salt or copper complex and (iii) at least one compound having an ionic halogen atom, a redox system comprising 1-benzyl-5-phenylbarbituric acid, copper acetylacetonate and benzyldibutylammonium chloride is particularly preferred.
- the polymerization in the 2-component prosthesis base material is particularly preferably started via a barbituric acid derivative.
- suitable initiators for the polymerization reaction of cold- or autopolymerizing starting mixtures are those with which free-radical polymerization reactions can be started.
- Preferred initiators are peroxides and azo compounds such as the following: LPO: dilauroyl peroxide, BPO: Dibenzoyl peroxide, t-BPEH: tert-butyl per-2-ethylhexanoate, AIBN: 2,2'-azobis-(isobutyronitrile), DTBP: di-tert-butyl peroxide.
- Suitable activators e.g. As aromatic amines are added.
- suitable amines which may be mentioned are N,N-dimethyl-p-toluidine, N,N-dihydroxyethyl-p-toluidine and diethyl p-dibenzylaminobenzoate.
- the amines regularly function as co-initiators and are usually present in an amount of up to 0.5% by weight.
- the monomers, reactive diluents, initiators, additives and fillers are weighed out and homogenized with the aid of a speed mixer (Hauschild—DAC 600.1 FVZ) at 1500 rpm at normal pressure for 5 minutes.
- the fillers are weighed into the monomer mixture one after the other and the mixture is again homogenized in a speed mixer at 1500 rpm for 5 minutes under normal pressure.
- the composite is then homogenized again using a three-roll mill.
- the composite is again degassed in a speed mixer at 700 min -1 for 5 min in a vacuum.
- Determination of the flexural strength and the modulus of elasticity The production of the bending rods and the determination of the flexural strength and the modulus of elasticity (E modulus) are carried out according to DIN EN ISO 4049:2019, 7.11 on a test specimen with the dimensions 25 +/- 2 mm x 2.0 +/- 0.1 mm x 2.0 +/- 0.1 mm, the specimens are stored in water at 37 °C until the start of the measurement (light source: Kulzer, Translux Wave, with blue light (emission maximum approx. 440 to 460 nm), 700 mW/cm 2 , 20 s). 24 hours after irradiation, the test specimen is loaded at a crosshead speed of 0.75 +/- 0.25 mm/min or with an increase in load of 50 +/- 16 N/min up to the yield point or until fracture.
- the depth of cure/depth of polymerisation is determined in accordance with DIN EN ISO 4049:2019, 7.10 (light source: Translux 2Wave, 1200 mW/cm 2 , 20 s), cylindrical specimen greater than 6 mm in length, diameter 4 mm. If the If the depth of polymerisation is more than 3 mm, the specimen was at least 2 mm longer than the double specified polymerisation depth. The value of the depth of polymerisation given in this document therefore corresponds to the absolute value of the depth of polymerisation divided by two.
- Circular test specimens with a diameter of 20 mm and a thickness of 1 mm are produced from the composite paste by means of photopolymerization (light source: Kulzer, Translux Wave, 700 mW/cm 2 ).
- the colorimetric measurement of the test specimens is carried out using the Datacolor SF 800 device, with the test specimens being transparent against a black background.
- the composite is applied to a slide glass between a 1 mm high spacer ring and covered with a cover glass.
- the material sample wets the underside of the coverslip.
- the material sample is now irradiated from the underside using a light source (Kulzer Translux 2Wave, 1200 mW/cm 2 , 20s) and the deflection of the cover slip is determined using a laser from the top (Lit. Determination of polymerization shrinkage kinetics in visible-light -cured materials: methods development; DC Watts et al, Dental Materials, Oct. 1991, 281 ff).
- the double bond conversion U is determined using ATR-IR.
- a material sample is applied in a 2mm deep cylindrical form.
- the composite-filled cylindrical mold is placed on an ATR crystal, which is now on the underside of the material sample.
- An IR spectrum (wavelength range: 4000 cm -1 - 700 cm -1 ) is recorded.
- the composite is then covered on the upper side with a transparent film, irradiated using a light source (light source: Translux 2Wave, 1200 mW/cm 2 , 20 s) and another IR spectrum is recorded 10 minutes after the end of the photopolymerization.
- the quotient of the integral of the -C C- double bond signal (-1645 cm -1 ) before and after photopolymerization gives the residual double bond content, from which the double bond conversion L/ is determined in %.
- Method Determination of particle sizes The particle sizes can be determined using established testing methods, preferably using laser diffraction (DLS), SOP, MALVERN Mastersizer 2000. Other methods familiar to the person skilled in the art are defined in the standards ISO 22412:2017 Particle Size Analysis - Dynamic Light Scattering (DLS) or ISO 13320:2020 Particle Size Analysis - Laser Diffraction Methods.
- the particle sizes can be determined batchwise using DLS with the Zeta Sizer Advanced Range devices (0.3 nm to 15 microns) or continuously in an in-process control using the Zetasizer AT (0.3 nm to 10 microns) from Malvernpananalytical. D10, D50, D90 can also be determined using these methods.
- Viscosity The viscosity is preferably measured according to DIN 1342-2;2003-11 Newtonian liquids or DIN 1342-3;2003-11 non-Newtonian liquids with a rheometer (Anton Par, physicist NCR 301, viscosity ranges 200-3000 m-Pas at 100 /s 23 °C). examples
- the following dental composites were prepared and cured by means of photoinitiation (light source: Translux Wave (Kulzer), 1000 mW/cm 2
- Table 1a Composite formulations with a filler content of 68% by weight in the overall composition.
- Table 1b Composite formulations with a filler content of 68% by weight in the overall composition.
- Table 1c Composite formulations with a filler content of 68% by weight in the overall composition.
- Table 1d Composite formulations with a filler content of 68% by weight in the overall composition.
- Table 2 Composite formulations with varying proportions of fillers from 30 to 75% by weight in the overall composition.
- Table 3a Compositions - crosslinkers with different filler contents.
- Table 3b Properties of crosslinkers with different filler contents.
- Table 5a Examples according to the invention with monomers no. 1 and no. 2 as crosslinkers
- Table 5b Examples according to the invention
- Table 6 VG 1 to 5, examples 6 to 10 with thinner 6
- Table 7 VG 1 to 5, examples of crosslinkers 1+2 and thinner TEGDMA
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Abstract
L'invention concerne une composition polymérisable comprenant 0,01 à 90 % en poids d'au moins un composant de charge inorganique, 5 à 99,97 % en poids d'au moins deux uréthane acrylates, un uréthane acrylate correspondant à la formule I, et le second uréthane acrylate ayant au moins un groupe thiol uréthane bifonctionnel et au moins un groupe oléfinique, ainsi que des mélanges d'uréthane acrylates les comprenant, 0,01 à 25 % en poids d'au moins un monomère bi-, tri-, tétra-, ou multifonctionnel avec au moins un groupe éther, un groupe thioéther, et au moins un triester trifonctionnel et/ou un diester bifonctionnel, ledit diester étant choisi parmi le tricyclodécane diméthanol diméthacrylate et le tricyclodécane diméthanol diacrylate ou des mélanges desdits monomères bi-, tri-, tétra-, ou multifonctionnels, et 0,01 à 10 % en poids d'au moins un initiateur, un système initiateur et éventuellement au moins un stabilisant, et éventuellement au moins un pigment. La composition totale de la composition polymérisable est égale à 100 % en poids.
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PCT/EP2022/064194 WO2022248546A1 (fr) | 2021-05-27 | 2022-05-25 | Composition polymérisable contenant un groupe thiol uréthane |
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DE19803979C2 (de) * | 1998-01-28 | 2001-06-28 | Ivoclar Ag Schaan | Zusammensetzungen enthaltend Urethandi(meth)acrylat-Derivate von 1,3-Bis (1-isocyanato-1-methylethyl)benzol |
EP1722708A4 (fr) | 2004-03-09 | 2009-04-08 | Univ Colorado | Thiol oligomere reactif et matieres ene servant de melanges de restauration dentaire |
EP2910236B1 (fr) | 2014-02-24 | 2020-02-12 | Ivoclar Vivadent AG | Matériaux dentaires à base de thiols à faible odeur |
US10130563B2 (en) | 2014-03-31 | 2018-11-20 | Mitsui Chemicals, Inc. | Dental polymerizable monomer compositions |
DE102014116402A1 (de) * | 2014-11-11 | 2016-05-12 | Voco Gmbh | Verwendung radikalisch härtbarer Zusammensetzungen in generativen Fertigungsverfahren |
EP3427715B1 (fr) | 2017-07-14 | 2021-03-03 | Ivoclar Vivadent AG | Matière dentaire à base de monomère fluide pouvant être durci par polymérisation radicalaire ayant un indice de réfraction élevé |
JP6941186B2 (ja) | 2017-11-28 | 2021-09-29 | 三井化学株式会社 | (メタ)アクリレートおよびその用途 |
US11701304B2 (en) | 2017-12-26 | 2023-07-18 | Tokuyama Dental Corporation | Dental restorative material and resin material for dentistry cutting formed of same |
WO2020040141A1 (fr) | 2018-08-21 | 2020-02-27 | 三井化学株式会社 | (méth)acrylate, composition monomère pour matériau dentaire, corps moulé, composition pour matériau dentaire, matériau dentaire et procédé de production de (méth)acrylate |
CN113631602A (zh) * | 2019-03-29 | 2021-11-09 | 三井化学株式会社 | 光固化性组合物、固化物及牙科用制品 |
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2021
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2022
- 2022-05-25 WO PCT/EP2022/064194 patent/WO2022248546A1/fr active Application Filing
- 2022-05-25 JP JP2023573029A patent/JP2024520051A/ja active Pending
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