JP7016494B2 - Kit for preparing lining material composition for denture base - Google Patents
Kit for preparing lining material composition for denture base Download PDFInfo
- Publication number
- JP7016494B2 JP7016494B2 JP2017168123A JP2017168123A JP7016494B2 JP 7016494 B2 JP7016494 B2 JP 7016494B2 JP 2017168123 A JP2017168123 A JP 2017168123A JP 2017168123 A JP2017168123 A JP 2017168123A JP 7016494 B2 JP7016494 B2 JP 7016494B2
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- Prior art keywords
- resin particles
- meth
- acrylate
- mass
- polymerizable monomer
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 112
- 239000000203 mixture Substances 0.000 title claims description 78
- 239000002245 particle Substances 0.000 claims description 96
- -1 Tertiary amine compound Chemical class 0.000 claims description 88
- 239000000178 monomer Substances 0.000 claims description 81
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 74
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 239000011344 liquid material Substances 0.000 claims description 50
- 239000000843 powder Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 45
- 150000003839 salts Chemical class 0.000 claims description 31
- 230000002165 photosensitisation Effects 0.000 claims description 29
- 239000003504 photosensitizing agent Substances 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- NHCFFVMWVHFFSJ-UHFFFAOYSA-N 2-phenyliodoniobenzoate;hydrate Chemical compound O.[O-]C(=O)C1=CC=CC=C1[I+]C1=CC=CC=C1 NHCFFVMWVHFFSJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000047 product Substances 0.000 description 53
- 238000002156 mixing Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 238000000016 photochemical curing Methods 0.000 description 13
- 239000000975 dye Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000001588 bifunctional effect Effects 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000010954 inorganic particle Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000005548 dental material Substances 0.000 description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 7
- 210000000214 mouth Anatomy 0.000 description 7
- 230000037048 polymerization activity Effects 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical group CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- 210000004513 dentition Anatomy 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 210000002200 mouth mucosa Anatomy 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000036346 tooth eruption Effects 0.000 description 3
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 2
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VZBILKJHDPEENF-UHFFFAOYSA-M C3-thiacarbocyanine Chemical compound [I-].S1C2=CC=CC=C2[N+](CC)=C1C=CC=C1N(CC)C2=CC=CC=C2S1 VZBILKJHDPEENF-UHFFFAOYSA-M 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 239000000999 acridine dye Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 2
- CQZCVYWWRJDZBO-UHFFFAOYSA-N diphenyliodanium;nitrate Chemical compound [O-][N+]([O-])=O.C=1C=CC=CC=1[I+]C1=CC=CC=C1 CQZCVYWWRJDZBO-UHFFFAOYSA-N 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 2
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- 239000002562 thickening agent Substances 0.000 description 2
- IIJKHYBWZHCZFS-UHFFFAOYSA-N (4-fluorophenyl)boron;sodium Chemical compound [Na].[B]C1=CC=C(F)C=C1 IIJKHYBWZHCZFS-UHFFFAOYSA-N 0.000 description 1
- JZDQKBZKFIWSNW-UHFFFAOYSA-N (4-methoxyphenyl)-phenyliodanium Chemical compound C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 JZDQKBZKFIWSNW-UHFFFAOYSA-N 0.000 description 1
- CGGPPTKPILLONI-UHFFFAOYSA-N (4-methyl-4-propan-2-ylcyclohexa-1,5-dien-1-yl)-phenyliodanium Chemical compound C1=CC(C(C)C)(C)CC=C1[I+]C1=CC=CC=C1 CGGPPTKPILLONI-UHFFFAOYSA-N 0.000 description 1
- VQVGJEIVVJBMCV-UHFFFAOYSA-N (4-octoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 VQVGJEIVVJBMCV-UHFFFAOYSA-N 0.000 description 1
- MHMPFHGJSJOKIV-UHFFFAOYSA-N (4-phenoxyphenyl)-phenyliodanium Chemical compound C=1C=C([I+]C=2C=CC=CC=2)C=CC=1OC1=CC=CC=C1 MHMPFHGJSJOKIV-UHFFFAOYSA-N 0.000 description 1
- RGXLDQDGZYZGEE-UHFFFAOYSA-N (4-tert-butylphenyl)-phenyliodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=CC=C1 RGXLDQDGZYZGEE-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
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- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
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- GOBCFCQSBBPEMI-UHFFFAOYSA-N 2,4-diethoxythioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(OCC)=CC(OCC)=C3SC2=C1 GOBCFCQSBBPEMI-UHFFFAOYSA-N 0.000 description 1
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- WWOAFDCQCIRYLF-UHFFFAOYSA-N 2-(2-acridin-9-ylethenyl)phenol Chemical compound Oc1ccccc1C=Cc1c2ccccc2nc2ccccc12 WWOAFDCQCIRYLF-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- XSDSTTHDKZZVJZ-UHFFFAOYSA-N 2-(dimethylamino)fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(N(C)C)=CC=C3C2=C1 XSDSTTHDKZZVJZ-UHFFFAOYSA-N 0.000 description 1
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 1
- AKWFJQNBHYVIPY-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO AKWFJQNBHYVIPY-UHFFFAOYSA-N 0.000 description 1
- OWTQQPNDSWCHOV-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO OWTQQPNDSWCHOV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Dental Preparations (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、従来の光硬化性組成物に比べて硬化体の表面未重合が少なく、適度な弾性率を有し、しかも高い光硬化深さを有する硬化体物性が得られる光硬化性組成物からなる義歯床用裏装材組成物を調製するためのキットに関するものである。
INDUSTRIAL APPLICABILITY The present invention has a photocurable composition that has less surface unpolymerization of the cured product than the conventional photocurable composition, has an appropriate elastic modulus, and can obtain a cured product having a high photocuring depth. It relates to a kit for preparing a backing material composition for a prosthesis bed made of a material.
光照射によりラジカルまたはイオン種を発生し、重合性の不飽和化合物や環状化合物を重合させる光重合開始剤に関しては、種々の提案がなされている。一般的には、光を吸収することによりそれ自身が分解して重合活性種を生成する化合物や、さらに適当な増感剤を組み合わせた系が広く検討され、使用されている。 Various proposals have been made for photopolymerization initiators that generate radicals or ionic species by light irradiation to polymerize polymerizable unsaturated compounds and cyclic compounds. In general, a system in which a compound that decomposes itself to produce a polymerization active species by absorbing light and a suitable sensitizer are combined has been widely studied and used.
前者の例としては、アシルフォスフィンオキサイド化合物やα-ジケトン化合物が知られており、特にα-ジケトン化合物は、人体に対して影響の少ない可視光の波長領域で重合開始能を示す(例えば、代表的なα-ジケトン化合物であるカンファーキノンは、極大吸収波長が468nmにある黄色の化合物である)。また、後者の例としては、α-ジケトン化合物と第三級アミン化合物との組み合わせがよく知られ、このような組み合わせは、α-ジケトン化合物が可視光の波長領域で重合開始能を示すことから、歯科用材料の分野で有用に用いられている。 As an example of the former, an acylphosphine oxide compound and an α-diketone compound are known, and in particular, the α-diketone compound exhibits a polymerization initiation ability in a wavelength region of visible light having little effect on the human body (for example,). Camphorquinone, which is a typical α-diketone compound, is a yellow compound having a maximum absorption wavelength of 468 nm). Further, as an example of the latter, a combination of an α-diketone compound and a tertiary amine compound is well known, and such a combination is because the α-diketone compound exhibits a polymerization initiation ability in the wavelength region of visible light. , Used usefully in the field of dental materials.
歯科用材料の分野において、上記のような光重合開始剤は、例えば、粉材に樹脂粒子、液材に重合性単量体を主成分とするような粉液型の義歯床用裏装材組成物を光重合するために使用されている。光重合して得られる義歯床用裏装材は、粉材と液材を混ぜたペースト(義歯床用裏装材組成物)を義歯上に盛りつけ、口腔粘膜との適合を得たのち口腔外で、専用の光照射器により光を照射して該ペーストを硬化させて使用される。以下、重合硬化させるために照射する光を「活性光」と呼ぶことがある。一般に、このような活性光は、360~500nm程度の波長域(α-ジケトン化合物の主たる吸収域である)における光強度が100~6000mW/cm2程度の出力の光源が用いられる。例えば、歯科医院において、光重合開始剤が配合された義歯床用裏装材組成物のペーストを、適合が悪くなった義歯に盛上げ、口腔内との適合を測った後、専用の光照射器を用いて活性光を照射して重合硬化させて義歯床用裏装材を作製し、義歯の修復が行われている。この際、最終硬化前のゴム弾性が発現した状態の該義歯床用裏装材を口腔内から撤去するため、アンダーカットがある様な症例で患者が痛みを伴わず処置することが可能となる(例えば、非特許文献1参照)。 In the field of dental materials, the above-mentioned photopolymerization initiator is, for example, a powder-type prosthesis lining material having resin particles as a main component in the powder material and a polymerizable monomer as a main component in the liquid material. It is used to photopolymerize the composition. The denture base lining material obtained by photopolymerization is obtained by placing a paste (composition of denture base lining material), which is a mixture of powder and liquid material, on the denture to obtain compatibility with the oral mucosa and then outside the oral cavity. Then, the paste is cured by irradiating it with light by a dedicated light irradiator and used. Hereinafter, the light irradiated for polymerization curing may be referred to as "active light". Generally, for such active light, a light source having an output of about 100 to 6000 mW / cm 2 in a wavelength range of about 360 to 500 nm (which is the main absorption range of the α-diketone compound) is used. For example, in a dental clinic, a paste of a denture base material composition containing a photopolymerization initiator is applied to a denture that has become incompatible, and after measuring the compatibility with the oral cavity, a dedicated light irradiator is used. The denture is repaired by irradiating the denture with active light and polymerizing and curing the denture base material. At this time, since the denture base lining material in which the rubber elasticity before the final curing is developed is removed from the oral cavity, it becomes possible for the patient to treat the case with undercut without pain. (See, for example, Non-Patent Document 1).
前記のように、光重合して得られる義歯床用裏装材を含む歯科用材料は、光硬化の際に、空気中の酸素により重合阻害が生じ、硬化体の表面に未重合層が形成され易い。歯科用材料において、未重合層が存在すると、食渣が付着し易くなったり、残留モノマーによる口腔内の炎症につながったりする場合がある。さらに、義歯床用裏装材に未重合層があると、硬化体(義歯床用裏装材)の研磨・削合を行う際に、未重合層が研磨バーに絡みつくために研磨性が低下する他、除去すると口腔内との適合性が悪くなるといった課題があった。 As described above, in the dental material including the denture base lining material obtained by photopolymerization, polymerization inhibition occurs due to oxygen in the air during photocuring, and an unpolymerized layer is formed on the surface of the cured product. Easy to do. In dental materials, the presence of an unpolymerized layer may facilitate the adhesion of food residue or lead to inflammation in the oral cavity due to residual monomers. Further, if the denture base backing material has an unpolymerized layer, the unpolymerized layer is entangled with the polishing bar when polishing and grinding the cured product (denture base backing material), resulting in reduced polishability. In addition, there is a problem that compatibility with the oral cavity deteriorates when it is removed.
この未重合層の課題を解決するために、様々な検討がなされている。例えば、光重合開始剤としてアリールヨードニウム塩、増感用化合物、及び電子供与体化合物を含んでなる組成を用いることで、重合度を高めて未重合を減らすことができる(特許文献1~3参照)。この方法によれば、未重合層を少なくできるため、歯科用材料を製造する際に適用し易い。 Various studies have been made to solve the problem of the unpolymerized layer. For example, by using a composition containing an aryliodonium salt, a sensitizing compound, and an electron donor compound as a photopolymerization initiator, the degree of polymerization can be increased and unpolymerized can be reduced (see Patent Documents 1 to 3). ). According to this method, the number of unpolymerized layers can be reduced, so that it is easy to apply when producing a dental material.
しかしながら、特許文献1~3に記載の方法では、重合度が高く、得られる硬化体が硬くなりすぎる傾向にあり、義歯床用裏装材として該硬化体は使用し難くなるといった問題があった。すなわち、義歯床用裏装材として使用するには、咀嚼時の応力を緩和するためには、適度な弾性率(柔らかさ)を有していなければ、使用し難いといった問題があり、特許文献1~3に記載の方法においては、この点で改善の余地があった。 However, the methods described in Patent Documents 1 to 3 have a problem that the degree of polymerization is high and the obtained cured product tends to be too hard, which makes it difficult to use the cured product as a backing material for a denture base. .. That is, in order to use it as a backing material for a denture base, there is a problem that it is difficult to use it unless it has an appropriate elastic modulus (softness) in order to relieve stress during mastication. In the methods described in 1 to 3, there was room for improvement in this respect.
以上のような未重合層の問題、および義歯床裏装材として使用を考慮した際、以下のような方法も提案されている。具体的には、義歯床裏装材を製造するに際し、光硬化の際に硬化体表面を空気にさらされないようにすることで、硬化体の表面に生じる未重合を減少させる方法である(非特許文献1)。この方法によれば、適度な弾性率を有し、未重合層を低減できるため、裏装材用途に適した硬化体を製造できる。 Considering the above-mentioned problems of the unpolymerized layer and its use as a denture base lining material, the following methods have also been proposed. Specifically, it is a method of reducing the unpolymerization generated on the surface of the cured product by preventing the surface of the cured product from being exposed to air during photo-curing in the production of the denture base lining material (non-polymerization). Patent Document 1). According to this method, since it has an appropriate elastic modulus and can reduce the unpolymerized layer, it is possible to produce a cured product suitable for use as a backing material.
しかしながら、非特許文献1に記載の方法では、口腔内での適合を得たのち裏装面全体にエアーバリア膜を塗布しなければならず、術者の操作が煩雑になってしまうという点で改善の余地があった。 However, in the method described in Non-Patent Document 1, it is necessary to apply an air barrier membrane to the entire backing surface after obtaining compatibility in the oral cavity, which complicates the operator's operation. There was room for improvement.
さらに、近年の超高齢化社会では、顎堤が著しく吸収した症例が増え、一度の裏装厚みが多くなる傾向にある。この場合特に、硬化体の弾性を適度に有しながら、深い地点での硬化性を十分に担保しなければならないが、このような光硬化型の裏装材組成物は存在していなかったのが現状である。 Furthermore, in the super-aging society in recent years, the number of cases in which the ridge is remarkably absorbed increases, and the thickness of the lining at one time tends to increase. In this case, in particular, it is necessary to sufficiently secure the curability at a deep point while having an appropriate elasticity of the cured product, but such a photocurable backing material composition did not exist. Is the current situation.
本発明の目的は、硬化体の表面未重合を低減し、適度な弾性を有し、しかも高い光硬化深さを達成することができる光硬化性組成物を提供することにあり、特に光硬化型の義歯床用裏装材に好適に用いることができる光硬化性組成物を提供することにある。 An object of the present invention is to provide a photocurable composition capable of reducing surface unpolymerization of a cured product, having appropriate elasticity, and achieving a high photocuring depth, and in particular, photocuring. It is an object of the present invention to provide a photocurable composition which can be suitably used as a backing material for a mold prosthesis.
本発明者らは上記課題を解決すべく鋭意検討を行った結果、光増感用化合物、第三級アミン化合物、アリールヨードニウム塩、および樹脂粒子を含む光硬化性組成物が上記課題を解決できることを見出した。その中でも、前記アリールヨードニウム塩が、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートを含む場合に、特に優れた効果が発揮されることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that a photocurable composition containing a photosensitizing compound, a tertiary amine compound, an aryliodonium salt, and resin particles can solve the above problems. I found. Among them, it has been found that when the aryliodonium salt contains diphenyliodonium-2-carboxylate monohydrate, a particularly excellent effect is exhibited, and the present invention has been completed.
即ち、本発明は、(a)光増感用化合物:0.01~10質量部、(b)第三級アミン化合物:0.02~5質量部、(c)アリールヨードニウム塩:0.01~5質量部、(d)(メタ)アクリレート系重合性単量体:100質量部、および(e)樹脂粒子:100~300質量部を含む光硬化性義歯床用裏装材組成物を調製するためのキットであって、前記(d)(メタ)アクリレート系重合性単量体の全量を含む液材と、前記(e)樹脂粒子の全量を含む粉材と、からなり、前記(b)第三級アミン化合物及び前記(c)アリールヨードニウム塩は前記液材に配合され、前記(a)光増感用化合物は前記粉材に配合され、前記液材に配合される前記(c)アリールヨードニウム塩は、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートである、ことを特徴とする、義歯床用裏装材組成物調製用キットである。
That is, in the present invention, (a) a photosensitizing compound : 0.01 to 10 parts by mass , (b) a tertiary amine compound : 0.02 to 5 parts by mass , and (c) an aryliodonium salt : 0.01 . A photocurable prosthesis backing material composition containing up to 5 parts by mass , (d) (meth) acrylate-based polymerizable monomer : 100 parts by mass , and (e) resin particles : 100 to 300 parts by mass was prepared. The kit comprises the above (d), a liquid material containing the entire amount of the (meth) acrylate-based polymerizable monomer, and the powder material containing the total amount of the (e) resin particles. () The tertiary amine compound and the (c) aryliodonium salt are blended in the liquid material, and the (a) photosensitizing compound is blended in the powder material and blended in the liquid material (c). The aryliodonium salt is a kit for preparing a backing material composition for an artificial tooth bed, characterized in that it is a diphenyliodonium-2-carboxylate monohydrate.
なお、義歯床用裏装材とは、一般的に、粉材と液材とを混合して硬化する前の形状を整えることができるもの、および硬化したものの両者を指す場合が多い。ただし、本発明においては、発明をより詳細に説明するために、硬化する前のものを義歯床用裏装材組成物(光硬化性組成物)とし、硬化後のものを義歯床用裏装材(硬化体)とする。 The denture base lining material generally refers to both a material that can be formed into a shape before being cured by mixing a powder material and a liquid material, and a material that is cured. However, in the present invention, in order to explain the invention in more detail, the one before curing is used as the denture base lining material composition (photocurable composition), and the one after curing is used as the denture base lining. Use as a material (cured body).
本発明の義歯床用裏装材組成物調製用キットによって調製される光硬化性義歯床用裏装材組成物(以下、「本発明の光硬化性組成物」と称す)は、それを重合硬化(光重合)して得らえる硬化体が、適度な弾性率を有し、表面未重合(硬化体表面の未重合の重合性単量体)が少なく、しかも深い地点での硬化性を高度に満たすものとなる。そのため、本発明の光硬化性組成物からなる硬化体は、義歯床用裏装材に使用できる。
The photocurable lining material composition for artificial dentition prepared by the kit for preparing the lining material composition for artificial dentition of the present invention (hereinafter referred to as "photocurable composition of the present invention") polymerizes it. The cured product obtained by curing (photopolymerization) has an appropriate elastic coefficient, has less surface unpolymerization (unpolymerized polymerizable monomer on the surface of the cured product), and has curability at a deep point. It will be highly satisfying. Therefore, the cured product made of the photocurable composition of the present invention can be used as a backing material for a denture base.
義歯床用裏装材は、適度な弾性率を有していることが求められる。それは、義歯に緩やかな応力が生じた場合にひずみ、瞬発的な応力が生じたときに破折しないためである。そのため、義歯床用裏装材に求められる弾性率は、1.0~2.0GPaであることが好ましく、1.2~1.8GPaであることがより好ましい。 The denture base lining material is required to have an appropriate elastic modulus. This is because the denture is distorted when a gentle stress is applied and does not break when a momentary stress is applied. Therefore, the elastic modulus required for the denture base lining material is preferably 1.0 to 2.0 GPa, more preferably 1.2 to 1.8 GPa.
本発明の光硬化性組成物は、(a)光増感用化合物、(b)第三級アミン化合物、(c)アリールヨードニウム塩、(d)重合性単量体、および(e)樹脂粒子を含む。以下、これら各成分について説明する。 The photocurable composition of the present invention comprises (a) a photosensitizing compound, (b) a tertiary amine compound, (c) an aryliodonium salt, (d) a polymerizable monomer, and (e) resin particles. including. Hereinafter, each of these components will be described.
(a)光増感用化合物
本発明における(a)光増感用化合物は、最大吸収波長を350~700nmに有し、活性光によりラジカルのような重合に有効な活性種を生成させる機能を有する化合物である。活性種は通常、重合性単量体または他の物質との間でエネルギー移動あるいは電子移動の結果生じる。
(A) Photosensitizing compound The (a) photosensitizing compound in the present invention has a maximum absorption wavelength of 350 to 700 nm and has a function of producing an active species effective for polymerization such as radicals by active light. It is a compound that has. Active species usually result from energy transfer or electron transfer with polymerizable monomers or other substances.
本発明における(a)光増感用化合物は、公知の光増感用化合物が何ら制限なく用いられる。本発明で好適に使用される光増感用化合物としては、ケトン化合物(特にα-ジケトン化合物)、クマリン系色素、シアニン系色素、メロシアニン系色素、チアジン系色素、アジン系色素、アクリジン系色素、キサンテン系色素、スクアリウム系色素及びピリリウム塩系色素等が挙げられ、とりわけα-ジケトン化合物のようなケトン化合物が好ましい。 As the (a) photosensitizing compound in the present invention, known photosensitizing compounds can be used without any limitation. Examples of the photosensitizing compound preferably used in the present invention include a ketone compound (particularly α-diketone compound), a coumarin dye, a cyanine dye, a merocyanine dye, a thiazine dye, an azine dye, and an acridine dye. Examples thereof include xanthene-based dyes, squalium-based dyes, pyrylium salt-based dyes, and the like, and a ketone compound such as an α-diketone compound is particularly preferable.
本発明で好適に使用される光増感用化合物を具体的に例示すれば、
カンファーキノン、9,10-フェナントレンキノン、ベンジル、ジアセチル、アセチルベンゾイル、2,3-ペンタジオン、2,3-オクタジオン、4,4‘-ジメトキシベンジル、アセナフテンキノン、4,4-ビス(ジメチルアミノ)ベンゾフェノン、9-フルオレノン、3,4-ベンゾ-9-フルオレノン、2-ジメチルアミノ-9-フルオレノン、2-メトキシ-9-フルオレノン、2-クロロ-9-フルオレノン、2,7-ジクロロ-9-フルオレノン、2-ニトロ-9-フルオレノン、2-アセトキシ-9-フルオレノン、ベンズアントロン、アントラキノン、2、4-ジヒドロキシベンゾフェノン等のケトン化合物;
3-チエノイルクマリン、3-(4-メトキシベンゾイル)クマリン、3-(4-シアノベンゾイル)クマリン、3-チエノイル-7-メトキシクマリン、3-ベンゾイル-7-メトキシクマリン、5,7-ジメトキシ-3-(4-メトキシベンゾイル)クマリン、3-アセチル-7-ジメチルアミノクマリン、7-ジエチルアミノ-3-(4-シアノベンゾイル)クマリン、7-ジエチルアミノ-3-(4-ジメチルアミノベンゾイル)クマリン、3-シンナモイル-7-ジエチルアミノクマリン、3-カルボキシ-7-ジエチルアミノクマリン、3-(4-カルボキシベンゾイル)-7-ジエチルアミノクマリン、3,3’-カルボニルビス(7-ジエチルアミノ)クマリン、2,3,6,7-テトラヒドロ-1,1,7,7-テトラメチル-10-(ベンゾチアゾイル)-11-オキソ-1H,5H,11H-[1ベンゾピラノ[6,7,8-ij]キノリジン、3,3’-カルボニルビス(5,7-)ジメトキシ3,3’-ビスクマリン,3-(2’-ベンズオキサゾイル)-7-ジエチルアミノクマリン、3-(5’-フェニルチアゾイル-2’)-7-ジエチルアミノクマリン、3,3’-カルボニルビス(4-シアノ-7-ジエチルアミノ)クマリン等のクマリン化合物;
1,3,3,1’,3,3’-ヘキサメチル-2,2’-インドシアニンパークロレート、1,3’-ジエチル-2,2’-キノ-セレナシアニンアイオダイド、1,1’-ジエチル-2,4’-キノシアニンアイオダイド、3,3’-ジエチル-2,2’-チアゾリノカルボシアニンアイオダイド、3,3’、9-トリエチル-5,5’-ジフェニル-2,2’-オキサカルボシアニンアイオダイド、3,3’-ジエチル-2,2’-チアカルボシアニンアイオダイド、1,1’-ジエチル-2,4’-キノカルボシアニンアイオダイド、3,3’-ジエチル-2,2’-オキサジカルボシアニンアイオダイド、3,3’-ジエチル-2,2’-(4,5,4’、5’-ジベンゾ)チアジカルボシアニンアイオダイド、3,3’-ジエチル-2,2‘-オキサトリカルボシアニンアイオダイド等のシアニン系色素;
3-エチル-5-[2-(3-メチル-2-チアゾリジニリデン)エチリデン]-2-チオ-2,4-オキサゾリジンジオン、3-カルボキシメチル-5-[2-(3-エチル-2-ベンゾチアゾリニリデン)エチリデン]ローダニン、3-エチル-5-[2-(3-エチル-4-メチル-2-チアゾリニリデン)エチリデン]ローダニン等のメロシアニン系色素;
メチレンブルー、チオニンクロライド等のチアジン系色素;
リボフラビン、1-アミノ-4-ニトロフェナジン等のアジン系色素;
1-アミノアクリジン、9-(2’-ヒドロキシスチリル)アクリジン、アクリルオレンジ、アクリジンイエロー等のアクリジン系色素;
ローダミン、フルオレセイン、ローズベンガル等のキサンテン系色素;ジヒドロ-3-[2-ヒドロキシ-3-(5-イソプロピル-3,8-ジメチル-1-アジレニル)-4-オキソ-2-シクロブテン-1-イリデン]-7-イソプロピル-1,4-ジメチルアズレニウムヒドロオキサイド,内部塩等のスクアリウム系色素;
トリフェニルピリリウムパークロレート、2,6-ビス(4-メチルフェニル)-4-(4-フェニルチオクロロパールクレート)等のピリリウム塩系色素が挙げられる。
Specific examples of the photosensitizing compound preferably used in the present invention include
Fluorenone, 9,10-phenanthrenone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl, acenaphtenquinone, 4,4-bis (dimethylamino) Benzophenone, 9-fluorenone, 3,4-benzo-9-fluorenone, 2-dimethylamino-9-fluorenone, 2-methoxy-9-fluorenone, 2-chloro-9-fluorenone, 2,7-dichloro-9-fluorenone , 2-Nitro-9-fluorenone, 2-acetoxy-9-fluorenone, benzanthron, anthraquinone, 2,4-dihydroxybenzophenone and other ketone compounds;
3-Thienoyl coumarin, 3- (4-methoxybenzoyl) coumarin, 3- (4-cyanobenzoyl) coumarin, 3-thienoyl-7-methoxy coumarin, 3-benzoyl-7-methoxy coumarin, 5,7-dimethoxy- 3- (4-Methoxybenzoyl) coumarin, 3-acetyl-7-dimethylamino kumarin, 7-diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3 -Cinnamoyl-7-diethylaminocoumarin, 3-carboxy-7-diethylaminocoumarin, 3- (4-carboxybenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (7-diethylamino) coumarin, 2,3,6 , 7-Tetrahydro-1,1,7,7-Tetramethyl-10- (benzothiazoyl) -11-oxo-1H, 5H, 11H- [1 benzopyrano [6,7,8-ij] quinolidine, 3, 3'-carbonylbis (5,7-) dimethoxy 3,3'-biscumarin, 3- (2'-benzoxazoyl) -7-diethylaminocoumarin, 3- (5'-phenylthiazoyl-2')- Cmarin compounds such as 7-diethylaminocoumarin, 3,3'-carbonylbis (4-cyano-7-diethylamino) coumarin;
1,3,3,1', 3,3'-hexamethyl-2,2'-indocyanine perchlorate, 1,3'-diethyl-2,2'-quino-selenacyanine iodide, 1,1'- Diethyl-2,4'-quinocyanine iodide, 3,3'-diethyl-2,2'-thiazolinocarbocyanine iodide, 3,3', 9-triethyl-5,5'-diphenyl-2, 2'-oxacarbocyanine iodide, 3,3'-diethyl-2,2'-thiacarbocyanine iodide, 1,1'-diethyl-2,4'-quinocarbocyanine iodide, 3,3'- Diethyl-2,2'-oxadicarbocyanine iodide, 3,3'-diethyl-2,2'-(4,5,4', 5'-dibenzo) thiadicarbocyanine iodide, 3,3'-Diethyl-2,2'-Cyanine dyes such as oxatricarbocyanine iodide;
3-Ethyl-5- [2- (3-Methyl-2-thiazolidinilidene) ethylidene] -2-thio-2,4-oxazolidinedione, 3-carboxymethyl-5- [2- (3-ethyl-) 2-Benzothiazolinidene) etylidene] Rhodanine, 3-ethyl-5-[2- (3-ethyl-4-methyl-2-thiazolinidene) ethylidene] Rhodanine and other merocyanine dyes;
Thiazine pigments such as methylene blue and thionin chloride;
Adin dyes such as riboflavin and 1-amino-4-nitrophenazine;
Acridine dyes such as 1-aminoacridines, 9- (2'-hydroxystyryl) acridine, acrylic orange, acridine yellow;
Xanthene dyes such as rhodamine, fluorescein, rose bengal; dihydro-3- [2-hydroxy-3- (5-isopropyl-3,8-dimethyl-1-azirenyl) -4-oxo-2-cyclobutene-1-iriden ] -7-Isopropyl-1,4-dimethylazulenium hydrooxide, internal salts and other squarium dyes;
Examples thereof include pyrylium salt-based dyes such as triphenylpyrylium perchlorate and 2,6-bis (4-methylphenyl) -4- (4-phenylthiochloropearl crate).
以上の中でも、カンファーキノン、9,10-フェナントレンキノン、ベンジル、ジアセチル、アセチルベンゾイル、2,3-ペンタジオン、2,3-オクタジオン、4,4‘-ジメトキシベンジル、アセナフテンキノン等のα-ジケトン化合物がより好ましい。 Among the above, α-diketone compounds such as camphorquinone, 9,10-phenanthrenequinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4'-dimethoxybenzyl and acenaftenquinone. Is more preferable.
また、以上に例示した(a)光増感用化合物は、1種のものを使用することもできるし、複数種類のものを使用することもできる。 Further, as the (a) photosensitizing compound exemplified above, one kind may be used, or a plurality of kinds may be used.
本発明の光硬化性組成物における光増感用化合物の使用量は、特に制限されないが、多すぎる場合は硬化体が軟らかくなる傾向にあり、少なすぎると重合が不十分となり機械的強度が得られなくなる傾向にある。そのため、(d)重合性単量体を配合して光硬化性組成物とする場合の、(a)光増感用化合物の配合量は、下記に詳述する(d)重合性単量体100質量部に対して0.01~10質量部であることが好ましく、より好ましくは0.03~5質量部である。なお、複数種の(a)光増感用化合物を使用する場合には、その合計量が前記範囲を満足すればよい。 The amount of the photosensitizing compound used in the photocurable composition of the present invention is not particularly limited, but if it is too large, the cured product tends to be soft, and if it is too small, polymerization becomes insufficient and mechanical strength is obtained. It tends to be impossible. Therefore, when (d) a polymerizable monomer is blended to form a photocurable composition, the blending amount of (a) the photosensitizing compound is described in detail below (d) the polymerizable monomer. It is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass. When a plurality of types (a) photosensitizing compounds are used, the total amount thereof may satisfy the above range.
(b)第三級アミン化合物
本発明において使用される(b)第三級アミン化合物は、所謂還元剤(或いは電子供与体)であり、重合促進機能を有する。該(b)第三級アミン化合物は、公知の化合物が何ら制限なく使用できる。具体的には、分子中に芳香族環を有する(b1)芳香族第三級アミン化合物や、分子中に芳香族環を有していない(b2)脂肪族第三級アミン化合物の何れも使用できる。中でも、臭気等の点から(b1)芳香族第三級アミン化合物を使用することが好ましい。
(B) Tertiary amine compound The (b) tertiary amine compound used in the present invention is a so-called reducing agent (or electron donor) and has a polymerization promoting function. As the tertiary amine compound (b), known compounds can be used without any limitation. Specifically, either (b1) an aromatic tertiary amine compound having an aromatic ring in the molecule or (b2) an aliphatic tertiary amine compound having no aromatic ring in the molecule is used. can. Above all, it is preferable to use (b1) an aromatic tertiary amine compound from the viewpoint of odor and the like.
代表的な(b1)芳香族第三級アミン化合物を例示すると、下記一般式(1)で示される芳香族第三級アミン化合物が挙げられる。 An example of a typical (b1) aromatic tertiary amine compound is an aromatic tertiary amine compound represented by the following general formula (1).
式中、R1、及びR2は、各々独立に、アルキル基であり、R3はアルキル基、アリール基、アルケニル基、アルコキシ基、又はアルキルオキシカルボニル基である。 In the formula, R 1 and R 2 are each independently an alkyl group, and R 3 is an alkyl group, an aryl group, an alkenyl group, an alkoxy group, or an alkyloxycarbonyl group.
上記アルキル基としては、炭素数1~6のものが好ましく、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、n-ヘキシル基等を挙げることができる。また、このアルキル基は、当然のことながら置換基を有している置換アルキル基であってもよく、このような置換アルキル基としては、フロロメチル基、2-フロロエチル基等のハロゲン置換アルキル基;2-ヒドロキシエチル基等の水酸基置換アルキル基などを例示することができる。そのため、例えば、R1、R2、及びR3は、フロロメチル基、2-フロロエチル等のハロアルキル基や、2-ヒドロキシエチル基等のヒドロキシアルキル基であってもよい。 The alkyl group preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an n-hexyl group. Further, the alkyl group may be a substituted alkyl group having a substituent as a matter of course, and as such a substituted alkyl group, a halogen-substituted alkyl group such as a fluoromethyl group or a 2-fluoroethyl group; Examples thereof include a hydroxyl group substituted alkyl group such as a 2-hydroxyethyl group. Therefore, for example, R 1 , R 2 , and R 3 may be a haloalkyl group such as a fluoromethyl group or 2-fluoroethyl group, or a hydroxyalkyl group such as a 2-hydroxyethyl group.
また、R3において、アリール基としては、フェニル基、p-メトキシフェニル基、p-メチルチオフェニル基、p-クロロフェニル基、4-ビフェニリル基等の炭素数6~12のものを挙げることができる。 Further, in R3 , examples of the aryl group include those having 6 to 12 carbon atoms such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group and a 4-biphenylyl group.
アルケニル基としては、ビニル基、アリル基、2-フェニルエテニル基等の炭素数2~12のものを挙げることができる。 Examples of the alkenyl group include those having 2 to 12 carbon atoms such as a vinyl group, an allyl group and a 2-phenylethenyl group.
アルコキシ基としては、メトキシ基、エトキシ基、ブトキシ基等の炭素数1~10のものを挙げることができる。 Examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.
アルキルオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基、アミルオキシカルボニル基、イソアミルオキシカルボニル基等のアルキルオキシ基部分の炭素数が1~10のものを挙げることができる。 Examples of the alkyloxycarbonyl group include those having an alkyloxy group portion having 1 to 10 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an amyloxycarbonyl group, and an isoamyloxycarbonyl group.
上記一般式(1)の芳香族第三級アミン化合物において、R1、及びR2は、炭素数1~6のアルキル基であることが好ましく、特に、炭素数1~3の非置換のアルキル基(例えばメチル基、エチル基、n-プロピル基)や、2-ヒドロキシエチル基等がより好適である。 In the aromatic tertiary amine compound of the general formula (1), R 1 and R 2 are preferably alkyl groups having 1 to 6 carbon atoms, and in particular, unsubstituted alkyl having 1 to 3 carbon atoms. A group (for example, a methyl group, an ethyl group, an n-propyl group), a 2-hydroxyethyl group and the like are more preferable.
また、R3は、アルキルオキシカルボニル基であることが好ましい。 Further, R 3 is preferably an alkyloxycarbonyl group.
このような(b1)芳香族第三級アミン化合物としては、p-ジメチルアミノ安息香酸メチル、p-ジメチルアミノ安息香酸エチル、p-ジメチルアミノ安息香酸プロピル、p-ジメチルアミノ安息香酸アミル、p-ジメチルアミノ安息香酸イソアミル、p-ジエチルアミノ安息香酸エチル、p-ジエチルアミノ安息香酸プロピル等が挙げられる。 Examples of such (b1) aromatic tertiary amine compounds include methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, and p-. Examples thereof include isoamyl dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate and the like.
また、上記一般式(1)で示される他の(b1)芳香族第三級アミン化合物としては、N,N-ジメチルアニリン、N,N-ジベンジルアニリン、N,N-ジメチル-p-トルイジン、N,N-ジエチル-p-トルイジン、N,N-ジ(β-ヒドロキシエチル)-p-トルイジン等が挙げられる。 Further, as the other (b1) aromatic tertiary amine compound represented by the above general formula (1), N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine , N, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine and the like.
前記(b)第三級アミン化合物として、前記一般式(1)で示される芳香族第三級アミン化合物、および/または、その他の芳香族第三級アミン化合物((b1)芳香族アミン化合物)を含むことにより、臭気が少なく、高い重合活性を示し、照射光による短時間での重合硬化性を維持し、尚且つ高い硬化体物性を発現させることができる。 As the (b) tertiary amine compound, the aromatic tertiary amine compound represented by the general formula (1) and / or other aromatic tertiary amine compound ((b1) aromatic amine compound). By containing the above, it is possible to exhibit low odor, high polymerization activity, maintain polymerization curability in a short time by irradiation light, and develop high cured body physical properties.
また、本発明においては、(b)第三級アミン化合物として、(b2)脂肪族第三級アミン化合物を使用することもできる。前記(b2)脂肪族第三級アミン化合物を具体的に例示すると、トリエタノールアミン、N-メチルジエタノールアミン、トリエチルアミン、トリブチルアミン、N,N-ジメチルアミノエチルメタクリレート、N,N-ジエチルアミノエチルメタクリレート等が挙げられる。 Further, in the present invention, (b2) an aliphatic tertiary amine compound can also be used as the (b) tertiary amine compound. Specific examples of the (b2) aliphatic tertiary amine compound include triethanolamine, N-methyldiethanolamine, triethylamine, tributylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate and the like. Can be mentioned.
これら(b)第三級アミン化合物は、1種で使用することもできるし、複数種(複数種の(b1)芳香族第三級アミン化合物、複数種の(b2)脂肪族第三級アミン化合物、並びに、(b1)芳香族第三級アミン化合物および(b2)脂肪族第三級アミン化合物の併用)のものを使用することもできる。中でも、臭気の問題、重合活性、短時間での重合性、および得られる硬化体の物性等を考慮すると、(b1)芳香族第三級アミン化合物のみを使用することが好ましく、特に、前記一般式(1)で示される(b1)芳香族第三級アミン化合物のみを使用することが好ましい。ただし、(b1)芳香族第三級アミン化合物は、1種であっても、複数種であってもよい。 These (b) tertiary amine compounds may be used alone, or may be used in a plurality of types (multiple types of (b1) aromatic tertiary amine compounds and a plurality of (b2) aliphatic tertiary amines. Compounds and (b1) aromatic tertiary amine compounds and (b2) aliphatic tertiary amine compounds in combination) can also be used. Above all, considering the problem of odor, polymerization activity, polymerizability in a short time, physical properties of the obtained cured product, etc., it is preferable to use only (b1) an aromatic tertiary amine compound, and in particular, the above-mentioned general. It is preferable to use only the aromatic tertiary amine compound (b1) represented by the formula (1). However, the (b1) aromatic tertiary amine compound may be one kind or a plurality of kinds.
本発明において、(b)第三級アミン化合物の配合割合は、弾性率の点から、(a)光増感用化合物100質量部に対して、10~1000質量部であることが好ましく、50~500質量部がより好ましい。また、(d)重合性単量体に対する(b)第三級アミン化合物の配合割合は、(d)重合性単量体100質量部に対して0.02~5質量部が好ましく、0.03~3質量部となる量がより好ましい。なお、複数種の(b)第三級アミン化合物を使用する場合には、その合計量が前記範囲を満足すればよい。 In the present invention, the blending ratio of (b) the tertiary amine compound is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of (a) the photosensitizing compound, preferably 50 parts by mass, from the viewpoint of elastic modulus. Up to 500 parts by mass is more preferable. The mixing ratio of (b) the tertiary amine compound to (d) the polymerizable monomer is preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of (d) the polymerizable monomer. An amount of 03 to 3 parts by mass is more preferable. When a plurality of types (b) tertiary amine compounds are used, the total amount thereof may satisfy the above range.
(c)アリールヨードニウム塩
本発明においては、(c)アリールヨードニウム塩(以下単に(c)アリールヨードニウム塩と記載することもある)を配合したことを特徴とする。アリールヨードニウム塩は光照射による開裂反応により下記式(2)に示す通り、酸(HX)が発生する。
(C) Aryl Iodonium Salt The present invention is characterized in that (c) an aryl iodonium salt (hereinafter, may be simply referred to as (c) aryl iodonium salt) is blended. The aryliodonium salt produces an acid (HX) as shown in the following formula (2) by a cleavage reaction by light irradiation.
前記式中、R4及びR5は、各々独立に、水素原子またはアルキル基である。また、X-はアリールヨードニウム塩の対アニオンであり、HXは上記式(2)に示す開裂反応において発生する酸である。 In the above formula, R 4 and R 5 are each independently a hydrogen atom or an alkyl group. Further, X − is a counter anion of the aryl iodonium salt, and HX is an acid generated in the cleavage reaction represented by the above formula (2).
本発明で使用するアリールヨードニウム塩は、特に制限されるものではないが、前記式(2)に示す開裂反応において、酸性度の低い酸を発生するアリールヨードニウム塩を使用することが好ましい。なお、酸性度の低い酸とは、水中での酸解離定数が-3.0以上となるものを指す。 The aryliodonium salt used in the present invention is not particularly limited, but it is preferable to use an aryliodonium salt that generates an acid having a low acidity in the cleavage reaction represented by the above formula (2). An acid having a low acidity means an acid having an acid dissociation constant of -3.0 or more in water.
本発明においては、(c)アリールヨードニウム塩、(a)光増感用化合物、(b)第三級アミン化合物と共存している光硬化性組成物に、活性光を照射して重合反応が開始すると、下記式(3)で示されるように、アリールラジカル及びアリールヨードニウム塩の対アニオンに由来する酸を発生する(例えば、非特許文献2参照)。 In the present invention, a photocurable composition coexisting with (c) an aryliodonium salt, (a) a photosensitizing compound, and (b) a tertiary amine compound is irradiated with active light to carry out a polymerization reaction. When started, as represented by the following formula (3), an acid derived from the counter anion of the aryl radical and the aryl iodonium salt is generated (see, for example, Non-Patent Document 2).
ここで発生した酸の酸性度が高いほど、カチオン重合の活性が高くなるがアミン化合物、特に(b)第三級アミン化合物が存在する場合は、該(b)第三級アミン化合物と該酸とが中和反応を起こし、塩を生じやすくなると考えられる。そして、その結果、重合活性が低下する傾向にあると考えられる。そのため、本発明で使用する(c)アリールヨウドニウム塩は、重合活性を考慮すると、開裂反応により生じる酸の水中(25℃)での酸解離定数が-2.0~10.0となるものを使用することが好ましい。 The higher the acidity of the acid generated here, the higher the activity of cationic polymerization. However, when an amine compound, particularly (b) a tertiary amine compound is present, the (b) tertiary amine compound and the acid are present. It is considered that the compound causes a neutralization reaction and is likely to generate a salt. As a result, it is considered that the polymerization activity tends to decrease. Therefore, the (c) aryliodonium salt used in the present invention has an acid dissociation constant of −2.0 to 10.0 in water (25 ° C.) of the acid generated by the cleavage reaction in consideration of the polymerization activity. It is preferable to use.
なお、種々の酸の水中(25℃)での酸解離定数を参考までに示すと、HCl(-3.7)、HBr(-4.1)、HNO3(-1.8)、クロロ酢酸(2.9)、安息香酸(4.2)、フェノール(9.9)である(非特許文献3を参照)。 For reference, the acid dissociation constants of various acids in water (25 ° C.) are shown as HCl (-3.7), HBr (-4.1), HNO 3 (-1.8), and chloroacetic acid. (2.9), benzoic acid (4.2), phenol (9.9) (see Non-Patent Document 3).
本発明で使用される(c)アリールヨードニウム塩は、以下の化合物が例示できる。具体的には、
ジフェニルヨードニウム、ビス(p-クロロフェニル)ヨードニウム、ジトリルヨードニウム、ビス(p-メトキシフェニル)ヨードニウム、ビス(p-tert-ブチルフェニル)ヨードニウム、p-イソプロピルフェニル-p-メチルフェニルヨードニウム、ビス(m-ニトロフェニル)ヨードニウム、p-tert-ブチルフェニルフェニルヨードニウム、p-メトキシフェニルフェニルヨードニウム、p-オクチルオキシフェニルフェニルヨードニウム、およびp-フェノキシフェニルフェニルヨードニウムから選ばれるカチオンと、
ニトレート、アセテート、クロロアセテート、カルボキシレート、およびフェノラートから選ばれるアニオンと、
からなる(c)アリールヨードニウム塩が挙げられる。なお、これら(c)アリールヨードニウム塩は、1種のものを使用することもできるし、複数種類のものを使用することもできる。
Examples of the (c) aryliodonium salt used in the present invention include the following compounds. In particular,
Diphenyliodonium, bis (p-chlorophenyl) iodinenium, ditriliodonium, bis (p-methoxyphenyl) iodinenium, bis (p-tert-butylphenyl) iodinenium, p-isopropylphenyl-p-methylphenyliodonium, bis (m-) Nitrophenyl) Iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, and cations selected from p-phenoxyphenylphenyliodonium,
With anions selected from nitrate, acetate, chloroacetate, carboxylate, and phenolate,
(C) Aryliodonium salt consisting of (c). As these (c) aryliodonium salts, one kind may be used, or a plurality of kinds may be used.
本発明においては、前記に例示した(c)アリールヨードニウム塩の中でも、入手の容易で、かつ硬化速度に優れる点から、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートを使用することが好ましい。 In the present invention, among the (c) aryliodonium salts exemplified above, it is preferable to use diphenyliodonium-2-carboxylate monohydrate because it is easily available and has an excellent curing rate.
本発明の光重合開始剤における(c)アリールヨードニウム塩の配合割合は、表面未重合量やヌープ硬度の点から、通常、(a)光増感用化合物100質量部に対して、10~1500質量部であることが好ましく、20~1000質量部がより好ましい。また、(c)アリールヨードニウム塩の配合割合は、重合性単量体100質量部に対して0.01~5質量部であることが好ましく、0.05~2質量部となることがより好ましい。なお、複数種の(c)アリールヨードニウム塩を使用する場合には、その合計量が前記範囲を満足すればよい。 The blending ratio of the (c) aryliodonium salt in the photopolymerization initiator of the present invention is usually 10 to 1500 with respect to 100 parts by mass of the (a) photosensitizing compound from the viewpoint of the amount of surface unpolymerized and the Knoop hardness. It is preferably parts by mass, more preferably 20 to 1000 parts by mass. The mixing ratio of (c) aryliodonium salt is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the polymerizable monomer. .. When a plurality of types (c) aryliodonium salts are used, the total amount thereof may satisfy the above range.
(d)重合性単量体
また、本発明の光硬化性組成物に配合される(d)重合性単量体としては、カチオン重合性単量体、及びラジカル重合性単量体を好適に使用することができ、重合活性の点から、ラジカル重合性単量体を使用することが特に好ましい。
(D) Polymerizable monomer Further, as the (d) polymerizable monomer blended in the photocurable composition of the present invention, a cationically polymerizable monomer and a radically polymerizable monomer are preferably used. It can be used, and it is particularly preferable to use a radically polymerizable monomer from the viewpoint of polymerization activity.
本発明の光硬化性組成物において、好適に使用されるラジカル重合性単量体としては、公知のラジカル重合性単量体が何ら制限なく挙げられる。中でも、得られる硬化体の機械的強度、および硬化体中における(e)樹脂粒子の分散性の観点から、(メタ)アクリレート系(メタクリレート系、またはアクリレート系)の重合性単量体が好適に用いられ、公知の重合性単量体が特に制限なく使用できる。 Examples of the radically polymerizable monomer preferably used in the photocurable composition of the present invention include known radically polymerizable monomers without any limitation. Above all, a (meth) acrylate-based (methacrylate-based or acrylate-based) polymerizable monomer is preferable from the viewpoint of the mechanical strength of the obtained cured product and the dispersibility of the (e) resin particles in the cured product. Used and known polymerizable monomers can be used without particular limitation.
(メタ)アクリレート系の重合性単量体は、歯科用に一般的に使用される公知の化合物が特に制限されず使用される。具体的には、1分子中に1つの(メタ)アクリレート基を有する単官能重合性単量体、1分子中に2つの(メタ)アクリレート基を有する2官能重合性単量体、1分子中に3つの(メタ)アクリレート基を有する3官能重合性単量体、1分子中に4つの(メタ)アクリレート基を有する4官能重合性単量体が挙げられる。なお、1分子中に5つ以上の(メタ)アクリレート基を有する高多官能重合性単量体を使用することもできるが、本発明の光硬化性組成物より得られる硬化体を義歯床用裏装材として使用する場合には、適度な弾性が必要になるため、該光硬化性組成物は、該高多官能重合性単量体を含まない方が好ましい。
以下、これら重合性単量体について説明する。
As the (meth) acrylate-based polymerizable monomer, a known compound generally used for dentistry is used without particular limitation. Specifically, a monofunctional polymerizable monomer having one (meth) acrylate group in one molecule, a bifunctional polymerizable monomer having two (meth) acrylate groups in one molecule, and one molecule in one molecule. Examples thereof include a trifunctional polymerizable monomer having three (meth) acrylate groups and a tetrafunctional polymerizable monomer having four (meth) acrylate groups in one molecule. Although a highly polyfunctional polymerizable monomer having five or more (meth) acrylate groups in one molecule can be used, the cured product obtained from the photocurable composition of the present invention can be used for artificial dentition. When used as a backing material, the photocurable composition preferably does not contain the highly polyfunctional polymerizable monomer because appropriate elasticity is required.
Hereinafter, these polymerizable monomers will be described.
<単官能重合性単量体>
本発明で好適に使用できる単官能重合性単量体を例示すると、
メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、メトキシエチレングリコール(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、n-オクタデシル(メタ)アクリレート、n-ドデシル(メタ)アクリレート、n-トリデシル(メタ)アクリレート、2-(メタ)アクリロキシエチルプロピオネート、エトキシエチレングリコール(メタ)アクリレート、アセトアセトキシエチル(メタ)アクリレート、アセトアセトキシプロピル(メタ)アクリレート、アセトアセトキシブチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート等が挙げられる。これら単官能重合性単量体は、1種で使用することもできるし、複数種類のものを使用することもできる。
<Monofunctional polymerizable monomer>
To exemplify a monofunctional polymerizable monomer that can be suitably used in the present invention,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, n-hexyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, n-octadecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, 2 -(Meta) acryloxyethyl propionate, ethoxyethylene glycol (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. Can be mentioned. These monofunctional polymerizable monomers may be used alone or may be used in a plurality of types.
<二官能重合性単量体>
本発明で好適に使用できる二官能重合性単量体を例示すると、
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ペンタエチレングリコールジ(メタ)アクリレート、ヘキサエチレングリコールジ(メタ)アクリレート、オクタエチレングリコールジ(メタ)アクリレート、ノナエチレングリコールジ(メタ)アクリレート、デカエチレングリコールジ(メタ)アクリレート、ウンデカエチレングリコールジ(メタ)アクリレート、ドデカエチレングリコールジ(メタ)アクリレート、トリデカエチレングリコールジ(メタ)アクリレート、テトラデカエチレングリコールジ(メタ)アクリレート、ペンタデカエチレングリコールジ(メタ)アクリレート、ヘキサデカエチレングリコールジ(メタ)アクリレート、ヘプタデカエチレングリコールジ(メタ)アクリレート、オクタデカエチレングリコールジ(メタ)アクリレート、ノナデカエチレングリコールジ(メタ)アクリレート、エイコサエチレングリコールジ(メタ)アクリレート、ヘネイコサエチレングリコールジ(メタ)アクリレート、ドコサエチレングリコールジ(メタ)アクリレート、トリコサエチレングリコールジ(メタ)アクリレート、テトラコサエチレングリコールジ(メタ)アクリレート、ペンタコサエチレングリコールジ(メタ)アクリレート、ヘキサコサエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,3-ブタンジオールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、1,12-ステアリルジ(メタ)アクリレート、2,2-ビス((メタ)アクリロキシフェニル)プロパン、2,2-ビス[4-(2-ヒドロキシ-3-(メタ)アクリロキシフェニル)]プロパン、2,2-ビス(4-(メタ)アクリロキシエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロキシジエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロキシプロポキシフェニル)プロパン等が挙げられる。これら二官能重合性単量体は、1種で使用することもできるし、複数種類のものを使用することもできる。
<Bifunctional polymerizable monomer>
To exemplify a bifunctional polymerizable monomer that can be suitably used in the present invention,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate , Octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, undecaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, tridecaethylene Glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, pentadecaethylene glycol di (meth) acrylate, hexadecaethylene glycol di (meth) acrylate, heptadecaethylene glycol di (meth) acrylate, octadecaethylene Glycoldi (meth) acrylate, Nonadeca ethylene glycol di (meth) acrylate, Eikosa ethylene glycol di (meth) acrylate, Heneikosa ethylene glycol di (meth) acrylate, Docosa ethylene glycol di (meth) acrylate, Tricosa ethylene Glycoldi (meth) acrylate, tetracosaethylene glycol di (meth) acrylate, pentacosa ethylene glycol di (meth) acrylate, hexacosa ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylic, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 9-Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-stearyldi (meth) acrylate, 2,2-bis ((meth) acryloxyphenyl) propane, 2, 2-Bis [4- (2-hydroxy-3- (meth) acryloxyphenyl)] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4-( Examples thereof include meta) acryloxidiethoxyphenyl) propane and 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane. These bifunctional polymerizable monomers may be used alone or in a plurality of types.
<三官能重合性単量体>
本発明で好適に使用できる三官能重合性単量体を例示すると、
トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールメタントリ(メタ)アクリレート等が挙げられる。これら三官能重合性単量体は、1種で使用することもできるし、複数種類のものを使用することもできる。
<Trifunctional polymerizable monomer>
To exemplify a trifunctional polymerizable monomer that can be suitably used in the present invention,
Examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolmethane tri (meth) acrylate. These trifunctional polymerizable monomers may be used alone or in a plurality of types.
<四官能重合性単量体>
本発明で好適に使用できる四官能重合性単量体を例示すると、ペンタエリスリトールテトラ(メタ)アクリレート等が挙げられる。
<Tetrafunctional polymerizable monomer>
Examples of the tetrafunctional polymerizable monomer that can be suitably used in the present invention include pentaerythritol tetra (meth) acrylate and the like.
<(d)重合性単量体における好適な配合割合>
本発明においては、(d)重合性単量体として、目的とする用途に応じて、各重合性単量体の配合割合を決定すればよい。そのため、前記単官能重合性単量体が100質量%とあってもよい。中でも、得られる硬化体を義歯床用裏装材として使用するためには、適度な弾性率が必要となるため、以下の配合割合とすることが好ましい。すなわち、弾性率の点から、(d)重合性単量体の全量を100質量%としたとき、単官能重合性単量体が40~70質量%、二官能重合性単量体が30~60質量%、三官能重合性単量体が0~10質量%、四官能以上の重合性単量体が0~10質量%であることが好ましく、さらには、単官能重合性単量体が50~70質量%、二官能重合性単量体が30~50質量%、三官能以上の重合性単量体が0質量%であることが好ましい。なお、前記の(a)光増感用化合物、(b)第三級アミン化合物、(c)アリールヨードニウム塩の配合割において、(d)重合性単量体お基準となる量は、重合性単量体の全量である。
<(D) Suitable compounding ratio in the polymerizable monomer>
In the present invention, (d) as the polymerizable monomer, the blending ratio of each polymerizable monomer may be determined according to the intended use. Therefore, the monofunctional polymerizable monomer may be 100% by mass. Above all, in order to use the obtained cured product as a backing material for a denture base, an appropriate elastic modulus is required, so the following compounding ratio is preferable. That is, from the viewpoint of elastic coefficient, (d) when the total amount of the polymerizable monomer is 100% by mass, the monofunctional polymerizable monomer is 40 to 70% by mass, and the bifunctional polymerizable monomer is 30 to 30%. It is preferable that the content is 60% by mass, the content of the trifunctional polymerizable monomer is 0 to 10% by mass, the content of the tetrafunctional or higher polymerizable monomer is 0 to 10% by mass, and the content of the monofunctional polymerizable monomer is 0 to 10% by mass. It is preferable that 50 to 70% by mass, the bifunctional polymerizable monomer is 30 to 50% by mass, and the trifunctional or higher polymerizable monomer is 0% by mass. In the compounding ratio of (a) the photosensitizing compound, (b) the tertiary amine compound, and (c) the aryliodonium salt, the reference amount of the (d) polymerizable monomer is polymerizable. The total amount of monomer.
本発明において使用する(d)重合性単量体の分子量は、特に制限されるものではないが、得られる硬化体を義歯床用裏装材として使用する場合には、重合活性が高く、機械的強度に優れ、かつ低刺激材料となる点から、(d)重合性単量体の全量を100質量%としたとき、分子量が150以上1000以下、より好適には180以上500以下のラジカル重合性単量体(好ましくは(メタ)アクリレート系重合性単量体)を、50質量%以上含有することが好ましく、70質量%以上含有することがより好ましく、100質量%とすることが好ましい。 The molecular weight of the (d) polymerizable monomer used in the present invention is not particularly limited, but when the obtained cured product is used as a backing material for a prosthesis bed, the polymerization activity is high and the machine has a high degree of polymerization activity. (D) Radical polymerization having a molecular weight of 150 or more and 1000 or less, more preferably 180 or more and 500 or less when the total amount of the polymerizable monomer is 100% by mass, because it has excellent physical strength and is a low irritant material. The content of the sex monomer (preferably (meth) acrylate-based polymerizable monomer) is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass.
(e)樹脂粒子
本発明の光硬化性組成物で好適に使用される(e)樹脂粒子としては、公知の樹脂粒子が何ら制限なく使用できる。この(e)樹脂粒子は、固体(粉)の状態で使用するものである。本発明においては、この(e)樹脂粒子を含むことにより、得られる硬化体を義歯床用裏装材として好適に使用できる。
(E) Resin particles As the (e) resin particles preferably used in the photocurable composition of the present invention, known resin particles can be used without any limitation. The (e) resin particles are used in a solid (powder) state. In the present invention, the obtained cured product can be suitably used as a backing material for a denture base by containing the resin particles (e).
本発明で好適に使用される(e)樹脂粒子としては、
ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸プロピル、ポリメタクリル酸ブチル、ポリメタクリル酸アミル、ポリメタクリル酸ヘキシル、メタクリル酸メチル-メタクリル酸エチル共重合体、エチレン-酢酸ビニル共重合体、ポリスチレン、スチレン-ブタジエン共重合体、アクリロニトリル-スチレン共重合体、アクリロニトリル-スチレン-ブタジエン共重合体等からなる(e1)非架橋型樹脂粒子が挙げられる。
As the resin particles (e) preferably used in the present invention,
Polymethylmethacrylate, ethylpolymethacrylate, propylpolymethacrylate, butylpolymethacrylate, amylpolymethacrylate, hexyl polymethacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene , (E1) Non-bridged resin particles composed of a styrene-butadiene copolymer, an acrylonitrile-styrene copolymer, an acrylonitrile-styrene-butadiene copolymer and the like.
また、本発明で好適に使用される(e)樹脂粒子としては、架橋型ポリメタクリル酸メチル、架橋型ポリメタクリル酸エチルからなる(e2)架橋型樹脂粒子等が挙げられる。 Further, examples of the (e) resin particles preferably used in the present invention include (e2) crosslinked resin particles made of crosslinked polymethylmethacrylate and crosslinked polyethylmethacrylate.
なお、(e1)非架橋型樹脂粒子と(e2)架橋型樹脂粒子とは、以下の方法で見分けることができる。例えば、(e1)非架橋型樹脂粒子は、良溶媒に溶解してしまうか、膨潤して見かけ上溶解するのに対して、(e2)架橋型樹脂粒子は、良溶媒中であってもほとんど膨潤することなく、粒子の形状を維持する。具体的には、本発明においては、1gの(e)樹脂粒子と50mlのテトラヒドロフラン(THF)とを、25℃で1時間攪拌混合した後、得られた混合液中に目視にて不溶分が存在しない(樹脂粒子が溶解している)ことが確認できた場合には、(e1)非架橋型樹脂粒子と見なすことができる。一方、(e2)架橋型樹脂粒子は、前記条件において得られた混合液中に不溶分が存在することになる。これら(e1)非架橋型樹脂粒子、および(e2)架橋型樹脂粒子は、公知の粒子であり、市販のものが何ら制限なく使用できる。 The (e1) non-crosslinked resin particles and the (e2) crosslinked resin particles can be distinguished by the following methods. For example, (e1) non-crosslinked resin particles either dissolve in a good solvent or swell and apparently dissolve, whereas (e2) crosslinked resin particles are mostly dissolved even in a good solvent. Maintains the shape of the particles without swelling. Specifically, in the present invention, 1 g of (e) resin particles and 50 ml of tetrahydrofuran (THF) are stirred and mixed at 25 ° C. for 1 hour, and then insoluble components are visually contained in the obtained mixed solution. When it is confirmed that the particles do not exist (the resin particles are dissolved), it can be regarded as (e1) non-crosslinked resin particles. On the other hand, in the (e2) crosslinked resin particles, an insoluble component is present in the mixed solution obtained under the above conditions. These (e1) non-crosslinked resin particles and (e2) crosslinked resin particles are known particles, and commercially available particles can be used without any limitation.
以上の(e)樹脂粒子は、1種で使用することもできるし、複数種類のものを使用することもできる。 The above (e) resin particles may be used alone or may be used in a plurality of types.
上記の中でも、得られる硬化体の弾性率や、(d)重合性単量体への溶解性(分散性)等の点から、(e)樹脂粒子((e1)非架橋型樹脂粒子、および(e2)架橋型樹脂粒子)は、(メタ)アクリレート系ポリマー((メタ)アクリレート系モノマーから得られるポリマー)からなる樹脂粒子であることが好ましい。さらには、機械的強度の観点から、(e)樹脂粒子は、炭素数が1~6のアルキル基、さらに好ましくは炭素数が1~4のアルキル基を有する(メタ)アクリレート系ポリマーからなる樹脂粒子であることが好ましい。 Among the above, (e) resin particles ((e1) non-crosslinked resin particles, and (e1) non-crosslinked resin particles, and so on, from the viewpoints of the elasticity of the obtained cured product, (d) solubility (dispersability) in the polymerizable monomer, and the like. The (e2) crosslinked resin particles) are preferably resin particles made of a (meth) acrylate-based polymer (a polymer obtained from a (meth) acrylate-based monomer). Further, from the viewpoint of mechanical strength, the (e) resin particles are made of a (meth) acrylate-based polymer having an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. It is preferably particles.
本発明において、使用する(e)樹脂粒子の粒径は特に限定されるものではない。中でも、一般的に歯科用途として使用されている、レーザー回折法で測定した平均粒子径(50%体積平均粒子径)が1~300μmの平均粒径の樹脂粒子であることが好ましい。その中でも、粉材と液材とのなじみの良さ、粘度上昇の観点から5~100μmの平均粒径の(e)樹脂粒子であることがより好ましい。また、平均粒径の異なる複数の充填剤を併用してもよい。また、(e)樹脂粒子の形状は特に制限されず、球状、不定形のいずれであってもよい。 In the present invention, the particle size of the (e) resin particles used is not particularly limited. Above all, it is preferable that the resin particles have an average particle size of 1 to 300 μm, which is generally used for dental purposes and has an average particle size (50% volume average particle size) measured by a laser diffraction method. Among them, (e) resin particles having an average particle size of 5 to 100 μm are more preferable from the viewpoint of good compatibility between the powder material and the liquid material and an increase in viscosity. Further, a plurality of fillers having different average particle sizes may be used in combination. Further, the shape of the resin particles (e) is not particularly limited and may be spherical or amorphous.
前記(e)樹脂粒子は、前記の通り、必要に応じて複数の種類のものを併用して使用することができる。中でも、得られる硬化体を義歯床用裏装材として使用する場合、弾性率の点から、(e)樹脂粒子の全量を100質量%としたとき、(e1)非架型橋樹脂粒子が90~100質量%、(e2)架橋型樹脂粒子が0~10質量%であることが好ましく、さらには、(e1)非架型橋樹脂粒子が100質量%、(e2)架橋型樹脂粒子が0質量%であることが好ましい。 As described above, the resin particles (e) can be used in combination of a plurality of types as needed. Above all, when the obtained hardened material is used as a backing material for a prosthesis bed, (e1) non-bridge resin particles are 90 when the total amount of (e) resin particles is 100% by mass from the viewpoint of elasticity. It is preferable that the content is ~ 100% by mass, (e2) the crosslinked resin particles are 0 to 10% by mass, further, (e1) the non-bridged bridge resin particles are 100% by mass, and (e2) the crosslinked resin particles are 0. It is preferably mass%.
さらに、(e1)非架橋樹脂粒子の中でも、得られる硬化体の機械的強度や液材への溶解性や膨潤性の点から、ゲルパーミネーションクロマトグラフィー(GPC)により測定した重量平均分子量が3~200万である樹脂粒子が好ましく、5~100万の範囲である樹脂粒子がより好ましい。 Further, among the (e1) non-crosslinked resin particles, the weight average molecular weight measured by gel permeation chromatography (GPC) is 3 from the viewpoint of the mechanical strength of the obtained cured product, the solubility in the liquid material, and the swellability. Resin particles in the range of up to 2 million are preferable, and resin particles in the range of 5 to 1 million are more preferable.
本発明の光硬化性組成物において、(e)樹脂粒子の配合割合は、得られる硬化体の弾性率の点から、(d)重合性単量体100質量部に対して、100~300質量部とすることが好ましい。特に、得られる硬化体を義歯床用裏装材として使用する場合には、150~250質量部とすることが好ましい。 In the photocurable composition of the present invention, the mixing ratio of (e) resin particles is 100 to 300% by mass with respect to (d) 100 parts by mass of the polymerizable monomer from the viewpoint of the elastic modulus of the obtained cured product. It is preferable to use a part. In particular, when the obtained cured product is used as a backing material for a denture base, it is preferably 150 to 250 parts by mass.
<その他 配合剤>
本発明の光硬化性組成物には、本発明の効果を損なわない範囲で他の公知の重合開始剤を配合することもできる。他の重合開始剤成分としては、
過酸化ベンゾイル、クメンハイドロパーオキサイド等の有機過酸化物類;
酸化バナジウム(IV)アセチルアセトナート、ビス(マルトラート)オキソバナジウム(IV)等の+IV価又は+V価のバナジウム化合物類;
テトラフェニルホウ素ナトリウム、テトラフェニルホウ素トリエタノールアミン塩、テトラフェニルホウ素ジメチル-p-トルイジン塩、テトラキス(p-フルオロフェニル)ホウ素ナトリウム、ブチルトリ(p-フルオロフェニル)ホウ素ナトリウム等のアリールボレート化合物類;
ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、ビス(2,6-ジメトキシベンソイル)-2,4,4-トリメチルペンチルホスフィンオキサイド等のアシルフォスフィンオキサイド類;ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル等のベンゾインアルキルエーテル類;
2,4-ジエトキシチオキサンソン、2-クロロチオキサンソン、メチルチオキサンソン等のチオキサンソン誘導体;
ベンゾフェノン、p,p’-ビス(ジメチルアミノ)ベンゾフェノン、p,p’-ジメトキシベンゾフェノン等のベンゾフェノン誘導体類等が挙げられる。
<Other compounding agents>
Other known polymerization initiators may be added to the photocurable composition of the present invention as long as the effects of the present invention are not impaired. As another polymerization initiator component,
Organic peroxides such as benzoyl peroxide and cumene hydroperoxide;
+ IV or + V vanadium compounds such as vanadium oxide (IV) acetylacetonate, bis (maltlate) oxovanadium (IV);
Arylborate compounds such as tetraphenylboron sodium, tetraphenylboron triethanolamine salt, tetraphenylboron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) boron sodium, butyltri (p-fluorophenyl) boron sodium;
Acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyle) -2,4,4-trimethylpentylphosphine oxide; benzoin methyl ether, benzoin Benzoylalkyl ethers such as ethyl ether and benzoinpropyl ether;
Thioxanson derivatives such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone, and methylthioxanthone;
Examples thereof include benzophenone derivatives such as benzophenone, p, p'-bis (dimethylamino) benzophenone, and p, p'-dimethoxybenzophenone.
また、本発明の光硬化性組成物には、本効果を損なわない範囲で公知の無機粒子を配合することもできる。代表的な無機粒子を具体的に例示すれば、石英、シリカ、アルミナ、シリカチタニア、シリカジルコニア、ランタンガラス、バリウムガラス、ストロンチウムガラス等が挙げられる。さらに無機粒子の内、カチオン溶出性無機粒子としては、水酸化カルシウム、水酸化ストロンチウム等の水酸化物、酸化亜鉛、ケイ酸塩ガラス、フルオロアルミノシリケートガラス等の酸化物が挙げられる。これらもまた、一種または二種以上を混合して用いても何等差し支えない。 Further, the photocurable composition of the present invention may contain known inorganic particles as long as the effect is not impaired. Specific examples of typical inorganic particles include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, strontium glass and the like. Further, among the inorganic particles, examples of the cation-eluting inorganic particles include hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass and fluoroaluminosilicate glass. These may also be used alone or in admixture of two or more.
また、これら無機粒子に(d)重合性単量体を予め添加し、ペースト状にした後、重合させ、粉砕して得られる粒状の有機-無機複合粒子を用いる場合もある。 Further, in some cases, granular organic-inorganic composite particles obtained by adding (d) a polymerizable monomer in advance to these inorganic particles to form a paste, polymerizing the particles, and pulverizing the particles may be used.
これら無機粒子の粒径は特に限定されず、一般的に歯科用材料として使用されている0.01μm~100μmの平均粒子径の粒子が目的に応じて適宜使用できる。また、粒子の屈折率も特に限定されず、一般的な歯科用粒子が有する1.4~1.7の範囲のものが制限なく使用できる。 The particle size of these inorganic particles is not particularly limited, and particles having an average particle size of 0.01 μm to 100 μm, which are generally used as dental materials, can be appropriately used depending on the intended purpose. Further, the refractive index of the particles is not particularly limited, and those in the range of 1.4 to 1.7 of general dental particles can be used without limitation.
さらに、上記した粒子の中でもとりわけ球状の無機粒子を用いると、得られる硬化体の表面滑沢性が増し、優れた修復材料となり得る。 Further, when spherical inorganic particles are used among the above-mentioned particles, the surface smoothness of the obtained cured product is increased, and it can be an excellent repair material.
上記した無機フィラーは、シランカップリング剤に代表される表面処理剤で処理することが、重合性単量体とのなじみをよくし、機械的強度や耐水性を向上させる上で望ましい。表面処理の方法は公知の方法で行えばよく、シランカップリング剤としては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルクロロシラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス(β-メトキシエトキシ)シラン、γ-メタクリロイルオキシプロピルトリメトキシシラン、γ-クロロプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、ヘキサメチルジシラザン等が好適に用いられる。 It is desirable to treat the above-mentioned inorganic filler with a surface treatment agent typified by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment method may be a known method, and examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, and vinyltriethoxysilane. Vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.
また、本発明の光硬化性組成物には、目的に応じその性能を低下させない範囲で水、有機溶媒や増粘剤等を添加することも可能である。当該有機溶媒としては、ヘキサン、ヘプタン、オクタン、トルエン、ジクロロメタン、メタノール、エタノール、酢酸エチル等があり、増粘剤としてはポリビニルピロリドン、カルボキシメチルセルロース、ポリビニルアルコール等の高分子化合物や高分散性シリカが例示される。 Further, it is also possible to add water, an organic solvent, a thickener, or the like to the photocurable composition of the present invention as long as the performance is not deteriorated according to the purpose. Examples of the organic solvent include hexane, heptane, octane, toluene, dichloromethane, methanol, ethanol, ethyl acetate and the like, and examples of the thickener include high molecular compounds such as polyvinylpyrrolidone, carboxymethyl cellulose and polyvinyl alcohol and highly dispersible silica. Illustrated.
<光硬化性組成物の硬化方法(光重合方法)>
本発明の光硬化性組成物を硬化させる際には、α-ジケトン系の光増感用化合物を硬化させるために用いられるのと同じ公知の光源を用いることができ、カーボンアーク、キセノンランプ、メタルハライドランプ、タングステンランプ、LED、ハロゲンランプ、ヘリウムカドミウムレーザー、アルゴンレーザー等の可視光線の光源が何ら制限なく使用される。照射時間は、光源の波長、強度、硬化体の形状や材質によって異なるため、予備的な実験によって予め決定しておけばよい。
<Curing method of photocurable composition (photopolymerization method)>
When the photocurable composition of the present invention is cured, the same known light source used for curing the α-diketone-based photosensitizing compound can be used, and carbon arcs, xenon lamps, and the like can be used. Visible light sources such as metal halide lamps, tungsten lamps, LEDs, halogen lamps, helium cadmium lasers, and argon lasers are used without limitation. Since the irradiation time varies depending on the wavelength and intensity of the light source, the shape and material of the cured product, it may be determined in advance by preliminary experiments.
<光硬化性組成物の用途(硬化体の用途)>
本発明の光硬化性組成物は、歯科用材料として用いることができるが、中でも光重合型の義歯床用裏装材組成物として使用することが好ましい。既に述べたように、本発明の光硬化性組成物を光重合して得られる硬化体は、義歯床用裏装材に好適に使用できる。すなわち、該硬化体は、表面未重合層が低減され、適度な弾性率を有し、しかも高い光硬化深さを有するものとなるため、特に義歯床用裏装材として使用できる。
<Use of photocurable composition (use of cured product)>
The photocurable composition of the present invention can be used as a dental material, but it is particularly preferable to use it as a photopolymerizable type denture base lining material composition. As described above, the cured product obtained by photopolymerizing the photocurable composition of the present invention can be suitably used as a backing material for a denture base. That is, the cured product has a reduced surface unpolymerized layer, has an appropriate elastic modulus, and has a high photocuring depth, and therefore can be particularly used as a backing material for a denture base.
<義歯床用裏装材組成物 キット>
光重合型の義歯床用裏装材組成物とは、口腔粘膜と適合が悪くなった義歯形態を修復する材料であり、一般には、重合性単量体と樹脂粒子を主成分とし、可視光の照射により重合硬化させるために光重合開始剤が配合されている。また、操作性を良好なものとするために、粉材と液材を混合して使うキット様であるものが多い。
<Backing material composition kit for denture base>
The photopolymerizable lining material composition for an artificial tooth bed is a material for repairing an artificial tooth morphology that is incompatible with the oral mucosa, and generally contains a polymerizable monomer and resin particles as main components and is visible light. A photopolymerization initiator is blended in order to carry out polymerization and curing by irradiation with. In addition, in order to improve operability, there are many kits that use a mixture of powder and liquid materials.
本発明の光硬化性組成物を義歯床用裏装材組成物として使用する場合にも、粉材((e)樹脂粒子を主成分とする)と、液材((d)重合性単量体を主成分とする)とのキットとすることが好ましい。 Even when the photocurable composition of the present invention is used as a backing material composition for a denture base, a powder material (mainly composed of (e) resin particles) and a liquid material ((d) polymerizable single amount). It is preferable to use a kit with the body as the main component).
粉材と液材からなる義歯床用裏装材の特徴は、混和時の粘度の経時変化であり、歯科医師等の使用者が所望のペースト性状に調整して使用することができる。このような粉液型の義歯床用裏装材組成物は、粉材と液材を混合した際に、(e)樹脂粒子が(d)重合性単量体へ徐々に膨潤・溶解し、レジン泥となる。よって、混和直後は(e)樹脂粒子の(d)重合性単量体への膨潤・溶解が少なく高流動であるが、(d)重合性単量体が(e)樹脂粒子に浸透していくに従って膨潤・溶解が進み粘度が上昇し、塑性変形する程度の状態を経て、塑性変形しない状態となる。 The characteristic of the denture base lining material composed of powder material and liquid material is the change in viscosity with time at the time of mixing, and a user such as a dentist can adjust the paste property to a desired value before use. In such a powder-type denture base lining material composition, when the powder material and the liquid material are mixed, (e) the resin particles gradually swell and dissolve in (d) the polymerizable monomer, and the resin particles gradually swell and dissolve. It becomes resin mud. Therefore, immediately after mixing, (e) the resin particles do not swell or dissolve in the (d) polymerizable monomer and are highly fluid, but (d) the polymerizable monomer permeates the (e) resin particles. As it goes on, swelling and melting progress, the viscosity increases, and after a state of plastic deformation, it becomes a state of no plastic deformation.
実際の使用を想定すると、粉材と液材とを20秒程度混和した後、所望のペースト性状になるまで待ってから義歯の上に盛上げる操作を行う。そのため、粉材に含まれる触媒類(光重合開始剤:(a)光増感用化合物、(b)第三級アミン化合物、および(c)アリールヨードニウム塩を含む)は混和の際に速やかに液材に溶解する必要がある。ここで、本発明の特徴の一つである(c)アリールヨードニウム塩は、固体であるものが多く、中には(d)重合性単量体に溶解しにくいものもある。したがって、本発明の義歯床用裏装材組成物調製用キットでは、(c)アリールヨードニウム塩は、液材に配合し、液材を調製する際に均一に溶解しておく。また、(e)樹脂粒子を主成分とする粉材に(a)光増感用化合物を配合し、(d)重合性単量体を主成分とする液材に(c)第三級アミン化合物を配合する。
Assuming actual use, after mixing the powder material and the liquid material for about 20 seconds, wait until the desired paste property is obtained, and then perform the operation of raising the powder material on the denture. Therefore, the catalysts (including the photopolymerization initiator: (a) a photosensitizing compound, (b) a tertiary amine compound, and (c) an aryliodonium salt) contained in the powder material are promptly mixed at the time of mixing. It needs to be dissolved in the liquid material. Here, many of the (c) aryliodonium salts, which are one of the features of the present invention, are solid, and some of them are difficult to dissolve in (d) the polymerizable monomer. Therefore, in the kit for preparing the backing material composition for the denture base of the present invention, (c) the aryliodonium salt is blended with the liquid material and uniformly dissolved when the liquid material is prepared . Further , (e) a powder material containing resin particles as a main component is mixed with (a) a photosensitizing compound, and (d) a liquid material containing a polymerizable monomer as a main component is (c) a tertiary amine. Blend the compound .
粉材と液材との混合割合は、特に制限されるものではなく、各部材に含まれる前記成分の含有量と、前記説明した粉材と液材の混合時のペースト性状を踏まえ、適宜決定すれば良いが、一般的には粉材(g)/液材(ml)=0.3/1~4.5/1の割合が好ましく、粉材(g)/液材(ml)=0.8/1~3.5/1の割合がより好ましく、粉材(g)/液材(ml)=1.5/1~2.5/1の割合がさらに好ましい。 The mixing ratio of the powder material and the liquid material is not particularly limited, and is appropriately determined based on the content of the component contained in each member and the paste properties at the time of mixing the powder material and the liquid material described above. However, in general, the ratio of powder material (g) / liquid material (ml) = 0.3 / 1 to 4.5 / 1 is preferable, and powder material (g) / liquid material (ml) = 0. The ratio of .8 / 1 to 3.5 / 1 is more preferable, and the ratio of powder material (g) / liquid material (ml) = 1.5 / 1 to 2.5 / 1 is even more preferable.
なお、本明細書中の各成分は、粉材と液材とを上記割合で混合したときに、各配合量を満たしているように粉材または液材に配合されていればよい。 It should be noted that each component in the present specification may be blended in the powder or liquid material so as to satisfy each blending amount when the powder material and the liquid material are mixed in the above ratio.
<義歯床用裏装材組成物 好適な配合剤>
また、本発明の光硬化性組成物を義歯床用裏装材組成物として使用する場合、口腔粘膜の色調に合わせるために、上述した各成分に加え、顔料、染料、紫外線に対する変色防止のために紫外線吸収剤を配合することもできる。その他、義歯床用裏装材として配合される公知の添加材を、本発明の効果に影響のない範囲で、本発明の光硬化性組成物に配合することもできる。
<Preferable compounding agent for denture base lining material composition>
When the photocurable composition of the present invention is used as a denture base lining material composition, in order to match the color tone of the oral mucosa, in addition to the above-mentioned components, to prevent discoloration due to pigments, dyes, and ultraviolet rays. It is also possible to add an ultraviolet absorber to the skin. In addition, a known additive compounded as a backing material for a denture base can be blended into the photocurable composition of the present invention as long as the effect of the present invention is not affected.
<義歯床用裏装材組成物 粉材と液材とを製造する方法、および粉材と液材との混合方法>
以上の各成分が配合されてなる粉材、および液材を製造する方法については、特に制限なく、公知の製造方法に準じて製造すればよい。具体的には、各々所定の配合成分を測り取り、均一の性状になるまで混合すればよい。混合に用いることのできる装置に関しても特に制限なく、公知のものが使用できる。例えば、粉材は揺動ミキサー、液材は撹拌羽根、また、全成分を最初から混合してペーストにしたものはプラネタリーミキサー等により、均一に混合することで製造できる。また、製造した粉材、液材は各々容器に保存しておけばよく、任意の量に小分けして保存してよい。全成分を最初から混合して得られるペーストは、混合したものをそのまま使用することが好ましい。
<Composition of backing material for denture base A method for producing a powder material and a liquid material, and a method for mixing the powder material and the liquid material>
The method for producing the powder material and the liquid material in which each of the above components is blended is not particularly limited, and may be produced according to a known production method. Specifically, each predetermined compounding component may be measured and mixed until uniform properties are obtained. There is no particular limitation on the device that can be used for mixing, and a known device can be used. For example, a powder material can be produced by a rocking mixer, a liquid material by a stirring blade, and a paste obtained by mixing all the components from the beginning by uniformly mixing them with a planetary mixer or the like. Further, the produced powder material and liquid material may be stored in a container, respectively, and may be divided into arbitrary amounts and stored. As the paste obtained by mixing all the components from the beginning, it is preferable to use the mixed paste as it is.
以上のようにして得られる粉材と液材とからなる、粉液型の義歯床用裏装材組成物の使用方法は、各形態に合わせて適宜粉材と液材を混和し使用すればよい。その一例として、使用直前にラバーカップ等に所望の量の液材と粉材とを量り取り、練和棒あるいはヘラ等を用いて均一なペーストになるまで練和して使用するとよい。 The method of using the powder liquid type denture base lining material composition composed of the powder material and the liquid material obtained as described above can be obtained by appropriately mixing the powder material and the liquid material according to each form. good. As an example, it is advisable to weigh a desired amount of liquid material and powder material in a rubber cup or the like immediately before use, and knead them with a kneading stick or a spatula until a uniform paste is obtained.
その後、光重合開始剤((a)光増感用化合物、(b)第三級アミン化合物、および(c)アリールヨードニウム塩を含む)が配合された義歯床用裏装材組成物のペーストを、適合が悪くなった義歯に盛上げ、口腔内との適合を測った後、専用の光照射器を用いて活性光を照射して重合硬化させて義歯床用裏装材を作製することができる。なお、本発明の光硬化性組成物は、それ自体が高度に重合できるため、表面未重合層が少なくなる。そのため、光硬化の際に硬化体表面を空気にさらされないようにしなくともよい。ただし、空気にさらさない方法を採用した場合には、より一層、表面未重合層を低減できることは当然である。 Then, a paste of the denture base backing material composition containing a photopolymerization initiator (including (a) a photosensitizing compound, (b) a tertiary amine compound, and (c) an aryliodonium salt) was applied. It is possible to prepare a denture base material by swelling the denture that has become incompatible and measuring the compatibility with the oral cavity, and then irradiating it with active light using a dedicated light irradiator to polymerize and cure it. .. Since the photocurable composition of the present invention can be highly polymerized by itself, the number of surface unpolymerized layers is reduced. Therefore, it is not necessary to prevent the surface of the cured product from being exposed to air during photo-curing. However, when a method not exposed to air is adopted, it is natural that the surface unpolymerized layer can be further reduced.
以下、本発明を具体的に説明するために、実施例、比較例を挙げて説明するが、本発明の技術的思想は、これらにより何ら制限されるものではない。なお、以下の実施例および比較例で用いた化合物の略称を以下に示す。 Hereinafter, in order to specifically explain the present invention, examples and comparative examples will be described, but the technical idea of the present invention is not limited thereto. The abbreviations of the compounds used in the following examples and comparative examples are shown below.
(a)光増感用化合物
CQ:カンファーキノン。
CC:3,3’-カルボニルビス(7-ジエチルアミノ)クマリン。
DiSC2:3,3’-ジエチル-2,2’-チアカルボシアニンアイオダイド。
(A) Photosensitizing compound CQ: camphorquinone.
CC: 3,3'-carbonylbis (7-diethylamino) coumarin.
DiSC2: 3,3'-diethyl-2,2'-thiacarbocyanine iodide.
(b)第三級アミン化合物
(b1)DMBE:p-ジメチルアミノ安息香酸エチル。
(b2)TM:トリエタノールアミン。
(B) Tertiary amine compound (b1) DMBE: ethyl p-dimethylaminobenzoate.
(B2) TM: Triethanolamine.
(c)アリールヨードニウム塩
DPICH:ジフェニルヨードニウム-2-カルボキシレートモノハイドレート。
DPIN:ジフェニルヨードニウムニトレート。
DPIC:ジフェニルヨードニウムクロリド。
DPIB:ジフェニルヨードニウムブロリド。
(C) Aryl iodonium salt DPICH: diphenyl iodonium-2-carboxylate monohydrate.
DPIN: Diphenyliodonium nitrate.
DPIC: Diphenyliodonium chloride.
DPIB: Diphenyliodonium brolide.
(d)重合性単量体
HPr:2-メタクリロキシエチルプルピオネート(単官能重合性単量体、分子量186)。
ND:1,9-ノナメチレンメタクリレート(二官能重合性単量体、分子量296)。
TT:トリメチロールプロパントリメタクリレート(三官能重合性単量体、分子量338)。
PT:ペンタエリスリトールテトラメタクリレート(四官能重合性単量体、分子量367)。
(D) Polymerizable monomer HPr: 2-methacryloxyethyl purpionate (monofunctional polymerizable monomer, molecular weight 186).
ND: 1,9-nonamethylene methacrylate (bifunctional polymerizable monomer, molecular weight 296).
TT: Trimethylolpropane trimethacrylate (trifunctional polymerizable monomer, molecular weight 338).
PT: Pentaerythritol tetramethacrylate (tetrafunctional polymerizable monomer, molecular weight 367).
(e)樹脂粒子
(e1)PEMA1:球状ポリエチルメタクリレート粒子(非架橋型、平均粒径35μm、 重量平均分子量50万)。
(e2)PEMA2:球状ポリエチルメタクリレート粒子(架橋型、平均粒径35μm)。
(e1)PBMA:球状ポリブチルメタクリレート粒子(非架橋型、平均粒径35μm、重量平均分子量50万)。
(e1)PHMA:球状ポリヘキシルメタクリレート粒子(非架橋型、平均粒径35μm、重量平均分子量50万)。
(e1)PS:球状ポリスチレン(非架橋型、平均粒径30μm、重量平均分子量40万)。
(E) Resin particles (e1) PEMA1: Spherical polyethyl methacrylate particles (non-crosslinked type, average particle size 35 μm, weight average molecular weight 500,000).
(E2) PEMA2: Spherical polyethyl methacrylate particles (crosslinked type, average particle size 35 μm).
(E1) PBMA: Spherical polybutyl methacrylate particles (non-crosslinked type, average particle size 35 μm, weight average molecular weight 500,000).
(E1) PHMA: Spherical polyhexyl methacrylate particles (non-crosslinked type, average particle size 35 μm, weight average molecular weight 500,000).
(E1) PS: Spherical polystyrene (non-crosslinked type, average particle size 30 μm, weight average molecular weight 400,000).
(f)その他成分
SiO2:球状シリカ(平均粒子径2μm)。
(F) Other components SiO 2 : Spherical silica (average particle diameter 2 μm).
評価方法
(1)硬化体の表面未重合量(未重合層)の測定
粉材と液材とを、粉材(g)/液材(ml)=2/1の割合でラバーカップ内に入れ、20秒間混和した。20×20×1mmのポリテトラフルオロエチレン製のモールドに、混和した光硬化性組成物(粉材と液材とを混合してなる光硬化性組成物)を流し込み、片面を大気中に曝した状態で歯科技工用光重合装置αライトV(MORITA社製)を用いて硬化体を作製した。得られた硬化体の厚みを5点測定後、エタノールに1分間浸漬し、未重合層を金属スパチュラで削合した。表面未重合層を除去した硬化体の厚みを測定し、エタノールに浸漬させる前の硬化体厚みの平均と金属スパチュラで除去した後の硬化体の厚みの平均との差を表面未重合層の厚さとした。
Evaluation method (1) Measurement of the surface unpolymerized amount (unpolymerized layer) of the cured product Put the powder material and the liquid material in a rubber cup at a ratio of powder material (g) / liquid material (ml) = 2/1. , 20 seconds mixed. A mixed photocurable composition (a photocurable composition obtained by mixing a powder material and a liquid material) was poured into a mold made of 20 × 20 × 1 mm polytetrafluoroethylene, and one side was exposed to the atmosphere. In this state, a cured product was prepared using a photopolymerizing device for dental technology α-light V (manufactured by MORITA). After measuring the thickness of the obtained cured product at 5 points, it was immersed in ethanol for 1 minute, and the unpolymerized layer was ground with a metal spatula. The thickness of the cured product from which the surface unpolymerized layer has been removed is measured, and the difference between the average thickness of the cured product before immersion in ethanol and the average thickness of the cured product after removal with a metal spatula is the thickness of the surface unpolymerized layer. I made it.
(2)硬化体の硬化深さの測定
粉材と液材とを、粉材(g)/液材(ml)=2/1の割合でラバーカップ内に入れ、20秒間混和した。内径9mmφ×肉厚2mm×高さ10mmのポリ塩化ビニル製のモールドに、混和した光硬化性組成物(粉材と液材とを混合してなる光硬化性組成物)を充填して両面をポリプロピレンフィルムで圧接した。歯科技工用光重合装置αライトV(MORITA社製)で同一方向から5分間光照射し、硬化体を作製した。得られた硬化体の光照射面と非照射面の表面硬硬度を微小硬度計(松沢精機製MHT-1型)にてヌープ圧子を用いて、荷重100gf、荷重時間20秒で硬化体にできたくぼみの長軸の対角線長さにより求めた。ここで、非照射面のヌープ硬度が7以上の場合は、深い地点まで硬化していると判断し、硬化判定を○、7未満の場合は硬化判定を×とした。
(2) Measurement of curing depth of the cured product The powder material and the liquid material were placed in a rubber cup at a ratio of powder material (g) / liquid material (ml) = 2/1 and mixed for 20 seconds. A mold made of polyvinyl chloride having an inner diameter of 9 mmφ × a wall thickness of 2 mm × a height of 10 mm is filled with a mixed photocurable composition (a photocurable composition obtained by mixing a powder material and a liquid material) on both sides. It was pressure-welded with a polypropylene film. A cured product was prepared by irradiating light from the same direction for 5 minutes with a dental technician photopolymerizer α-light V (manufactured by MORITA). The surface hardness of the light-irradiated surface and the non-irradiated surface of the obtained cured product can be measured with a micro-hardness meter (MHT-1 type manufactured by Matsuzawa Seiki) using a Knoop indenter with a load of 100 gf and a load time of 20 seconds. It was calculated by the diagonal length of the long axis of the depression. Here, when the Knoop hardness of the non-irradiated surface is 7 or more, it is determined that the surface has been cured to a deep point, and when the hardness is less than 7, the curing determination is determined to be x.
(3)硬化体の弾性率測定
粉材と液材とを、粉材(g)/液材(ml)=2/1の割合でラバーカップ内に入れ、20秒間混和した。30×30×2mmのポリテトラフルオロエチレン製のモールドに、混和した光硬化性組成物(粉材と液材とを混合してなる光硬化性組成物)を流し込み、両面を圧接した状態で歯科技工用光重合装置αライトV(MORITA社製)を用いて硬化体を作製した。次いで、#800および#1500の耐水研磨紙にて硬化体を研磨後、4×30×2mmの角柱状に試験片を切断後、この試験片を試験機(島津製作所製、オートグラフAG5000D)に装着し、支点間距離20mm、クロスヘッドスピード1mm/分で3点曲げ弾性率強度を測定した。
(3) Measurement of elastic modulus of the cured product The powder material and the liquid material were placed in a rubber cup at a ratio of powder material (g) / liquid material (ml) = 2/1 and mixed for 20 seconds. A mixed photocurable composition (a photocurable composition obtained by mixing a powder material and a liquid material) is poured into a mold made of 30 × 30 × 2 mm polytetrafluoroethylene, and both sides are pressed against each other for dentistry. A cured product was prepared using a photopolymerizing device for technical engineering, α-light V (manufactured by MORITA). Next, after polishing the cured product with # 800 and # 1500 water-resistant abrasive paper, the test piece was cut into a prism of 4 × 30 × 2 mm, and this test piece was used in a testing machine (manufactured by Shimadzu Corporation, Autograph AG5000D). It was mounted, and the 3-point flexural modulus strength was measured at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min.
<実施例1>
粉材として、(e)樹脂粒子(非架橋樹脂粒子) (e1):PEMA1(200質量部)、および(a)光増感用化合物:CQ(0.02質量部)を混合した。一方、液材として、(d)単官能重合性単量体:HPr(60質量部)、二官能重合性単量体:ND(40質量部)、(b)第三級アミン化合物 (b1)DMBE(0.5質量部)、および(c)アリールヨードニウム塩:DPICH(0.2質量部)を混合した。得られた粉材と液材とを前記評価方法(1)~(3)に記載した方法に従い硬化体を作製し、得られた硬化体の表面未重合量、光硬化深さ、および弾性率を評価した。
粉材と液材との組成を表1、および表2に示した。また、評価結果を表3に示した。
<Example 1>
As the powder material, (e) resin particles (non-crosslinked resin particles) (e1): PEMA1 (200 parts by mass) and (a) a photosensitizing compound: CQ (0.02 parts by mass) were mixed. On the other hand, as the liquid material, (d) monofunctional polymerizable monomer: HPr (60 parts by mass), bifunctional polymerizable monomer: ND (40 parts by mass), (b) tertiary amine compound (b1). DMBE (0.5 parts by mass) and (c) aryliodonium salt: DPICH (0.2 parts by mass) were mixed. A cured product of the obtained powder material and liquid material was prepared according to the methods described in the evaluation methods (1) to (3), and the surface unpolymerized amount, photocuring depth, and elastic modulus of the obtained cured product were prepared. Was evaluated.
The compositions of the powder material and the liquid material are shown in Tables 1 and 2. The evaluation results are shown in Table 3.
<実施例2~37>
粉材と液材との組成を表1、および表2に示すように変更した以外は、実施例1と同様により粉液型の光硬化性組成物(義歯床用裏装材組成物)を作製し、得られた光硬化性組成物(粉材と液材)を実施例1と同様の方法により硬化して硬化体を作製し、得られた硬化体を実施例1と同様の方法で評価した。
表面未重合量、光硬化深さ、および弾性率を評価した。結果を表3に示した。
<Examples 2-37>
A powder-liquid photocurable composition (lining material composition for artificial toothbed) was prepared in the same manner as in Example 1 except that the compositions of the powder material and the liquid material were changed as shown in Tables 1 and 2. The prepared and obtained photocurable composition (powder material and liquid material) was cured by the same method as in Example 1 to prepare a cured product, and the obtained cured product was cured by the same method as in Example 1. evaluated.
The amount of surface unpolymerized, the photocuring depth, and the elastic modulus were evaluated. The results are shown in Table 3.
<実施例38>
(d)重合性単量体:PEMA1(200質量部)、(a)光増感用化合物:CQ(0.3質量部)、(d)重合性単量体:HPr(60質量部)、(d)重合性単量体:ND(40質量部)、(b)第三級アミン化合物 (b1)DMBE(0.5質量部)、(c)アリールヨードニウム塩:DPICH(0.2質量部)を同時に混合して、1ペースト型の光硬化性組成物(義歯床用裏装材組成物)を作製し、前記評価方法(1)~(3)に記載の右方法に従い硬化体を作製した。該評価方法に従い得られた硬化体の表面未重合量、光硬化深さ、および弾性率を評価した。
その結果、表面未重合量が42μmとなり、ヌープ硬度が光照射面で8.3、非照射面で7.0となり硬化判定は○であった。また、弾性率も1.40GPaとなり、所望の機械的強度を得ることができた。
<Example 38>
(D) Polymerizable monomer: PEMA1 (200 parts by mass), (a) Photosensitizing compound: CQ (0.3 parts by mass), (d) Polymerizable monomer: HPr (60 parts by mass), (D) Polymerizable monomer: ND (40 parts by mass), (b) Tertiary amine compound (b1) DMBE (0.5 parts by mass), (c) Aryliodonium salt: DPICH (0.2 parts by mass) ) Are simultaneously mixed to prepare a 1-paste type photocurable composition (lining material composition for artificial tooth bed), and a cured product is prepared according to the right method described in the above evaluation methods (1) to (3). did. The surface unpolymerized amount, the photocuring depth, and the elastic modulus of the cured product obtained according to the evaluation method were evaluated.
As a result, the amount of unpolymerized surface was 42 μm, the Knoop hardness was 8.3 on the light-irradiated surface, and 7.0 on the non-irradiated surface, and the curing judgment was ◯. In addition, the elastic modulus was 1.40 GPa, and the desired mechanical strength could be obtained.
<比較例1~4>
粉材と液材との組成を、表1、および表2に示すように変更した以外は、実施例1と同様に光硬化性組成物(粉液型 義歯床用裏装材組成物)を作製し、実施例1と同様の方法により硬化体を作製した。さらに、実施例1と同様の方法により得られた硬化体の表面未重合量、光硬化深さ、および弾性率を評価した。結果を表3に示した。
<Comparative Examples 1 to 4>
A photocurable composition (powder-type denture base backing material composition) was used in the same manner as in Example 1 except that the compositions of the powder material and the liquid material were changed as shown in Tables 1 and 2. It was prepared, and a cured product was prepared by the same method as in Example 1. Further, the surface unpolymerized amount, the photocuring depth, and the elastic modulus of the cured product obtained by the same method as in Example 1 were evaluated. The results are shown in Table 3.
実施例1~16、21~37は、各成分が本発明で示される構成を満足するように配合されたものであるが、いずれの場合においても、表面未重合が少なく、高い光硬化深さが得られ、さらに義歯床用裏装材として所望の弾性率を示した。
In Examples 1 to 16 and 21 to 37, each component is blended so as to satisfy the configuration shown in the present invention, but in each case, there is little surface unpolymerization and a high photocuring depth. Was obtained, and further showed a desired elastic modulus as a backing material for a denture base.
実施例38の結果から、1ペースト型であっても、所望の機械的強度を有する硬化体が有られることが分かった。 From the results of Example 38, it was found that even a one-paste type has a cured product having a desired mechanical strength.
これに対し比較例1は、(a)光増感用化合物を配合しない場合であり、硬化しない。 On the other hand, Comparative Example 1 is a case where (a) a photosensitizing compound is not blended and does not cure.
比較例2は、(b)第三級アミン化合物を配合しない場合であり、表面未重合が増加し、十分な硬化深さも得られなかった。比較例3は本発明の特徴である(c)アリールヨードニウム塩を配合しない場合であり、表面未重合量が増加し、光硬化深さを得ることができない。 Comparative Example 2 was a case where (b) a tertiary amine compound was not blended, surface unpolymerization increased, and a sufficient curing depth could not be obtained. Comparative Example 3 is a case where the (c) aryliodonium salt, which is a feature of the present invention, is not blended, the amount of surface unpolymerized increases, and the photocuring depth cannot be obtained.
比較例4は、(e)樹脂粒子を無機粒子の球状SiO2に置き換えた場合であり、表面未重合量とヌープ硬度は向上するが、弾性率が著しく上昇した。 Comparative Example 4 is a case where (e) the resin particles are replaced with spherical SiO 2 of inorganic particles, and the surface unpolymerized amount and the Knoop hardness are improved, but the elastic modulus is remarkably increased.
Claims (5)
前記(d)(メタ)アクリレート系重合性単量体の全量を含む液材と、前記(e)樹脂粒子の全量を含む粉材と、からなり、
前記(b)第三級アミン化合物及び前記(c)アリールヨードニウム塩は前記液材に配合され、
前記(a)光増感用化合物は前記粉材に配合され、
前記液材に配合される前記(c)アリールヨードニウム塩は、ジフェニルヨードニウム-2-カルボキシレートモノハイドレートである、
ことを特徴とする、義歯床用裏装材組成物調製用キット。 (A) Photosensitizing compound : 0.01 to 10 parts by mass , (b) Tertiary amine compound : 0.02 to 5 parts by mass , (c) Aryliodonium salt : 0.01 to 5 parts by mass , ( d) A kit for preparing a backing material composition for a photocurable artificial tooth bed containing (meth) acrylate-based polymerizable monomer : 100 parts by mass and (e) resin particles : 100 to 300 parts by mass . hand,
It is composed of a liquid material containing the entire amount of the (d) (meth) acrylate-based polymerizable monomer and a powder material containing the entire amount of the (e) resin particles.
The (b) tertiary amine compound and the (c) aryl iodonium salt are blended in the liquid material.
The (a) photosensitizing compound is added to the powder material.
The (c) aryliodonium salt blended in the liquid material is diphenyliodonium-2-carboxylate monohydrate.
A kit for preparing a backing material composition for a denture base.
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JP2015007082A (en) | 2007-10-01 | 2015-01-15 | スリーエム イノベイティブ プロパティズ カンパニー | Orthodontic composition with polymeric fillers |
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