WO2020153269A1 - 光重合開始剤、光硬化性組成物、硬化物、及び、歯科材料 - Google Patents
光重合開始剤、光硬化性組成物、硬化物、及び、歯科材料 Download PDFInfo
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- WO2020153269A1 WO2020153269A1 PCT/JP2020/001570 JP2020001570W WO2020153269A1 WO 2020153269 A1 WO2020153269 A1 WO 2020153269A1 JP 2020001570 W JP2020001570 W JP 2020001570W WO 2020153269 A1 WO2020153269 A1 WO 2020153269A1
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- photopolymerization initiator
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 208000008312 Tooth Loss Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LLMJPMVOOFMTKY-UHFFFAOYSA-N [2-(3-hydroxypropyl)phenyl]-phenylmethanone Chemical compound OCCCC1=CC=CC=C1C(=O)C1=CC=CC=C1 LLMJPMVOOFMTKY-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005024 alkenyl aryl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005025 alkynylaryl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005015 aryl alkynyl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- OEYRKUSFKACRRP-UHFFFAOYSA-N benzoyl piperidine-1-carboxylate Chemical compound C1CCCCN1C(=O)OC(=O)C1=CC=CC=C1 OEYRKUSFKACRRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- FWQJLFDJWHTPCJ-UHFFFAOYSA-N cyclodecane;methanol Chemical compound OC.OC.C1CCCCCCCCC1.C1CCCCCCCCC1.C1CCCCCCCCC1 FWQJLFDJWHTPCJ-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003178 glass ionomer cement Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005351 kimble Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003829 resin cement Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
Definitions
- the present disclosure relates to a photopolymerization initiator, a photocurable composition, a cured product, and a dental material.
- Photopolymerization initiators are often used for the polymerization of dental curable compositions such as composite resins.
- the photopolymerization initiator may often include a photoradical generator such as camphorquinone (hereinafter, also referred to as CQ), a photobase generator, and the like.
- CQ camphorquinone
- a photobase generator and the like.
- CQ camphorquinone
- the combination of CQ and a tertiary amine is one of the modes widely used in dental photopolymerization initiators.
- Japanese Patent Laid-Open No. 2016-8221 discloses camphorquinone (CQ) as an example of a photopolymerization initiator used in a dental restorative material composition such as the above-mentioned dental composite resin (curable composition).
- CQ camphorquinone
- a combination of ⁇ /diketone and a tertiary amine such as ethyl N,N-dimethylaminobenzoate is disclosed.
- the composite resin When using a dental curable composition for a composite resin, the composite resin may be filled up to the deep position of the tooth because the tooth is deeply damaged depending on the application site. In such a case, it is considered important to properly polymerize the composite resin at a deep position of the tooth (that is, a high polymerization depth).
- the photopolymerization initiator material obtained by combining camphorquinone (CQ) and a tertiary amine as described in JP-A-2016-8221 is not considered sufficient in terms of polymerization depth.
- An object of the present disclosure is to provide a photopolymerization initiator capable of improving the polymerization depth of a photocurable composition, and a photocurable composition, a cured product and a dental material containing the photopolymerization initiator. ..
- Means for solving the above problems include the following aspects.
- the peroxide contains at least one selected from the group consisting of diacyl peroxide compounds, peroxyester compounds, hydroperoxide compounds, inorganic peroxides and alkyl peroxides ⁇ 1> to ⁇
- the photobase generator contains at least one selected from the group consisting of an oxime ester compound, an acyl compound, a carbamate compound, an aminoacetophenone compound, a tertiary amine compound, a quaternary ammonium salt compound and an amide compound ⁇
- the photopolymerization initiator according to any one of 1> to ⁇ 4>.
- ⁇ 6> The photopolymerization initiator according to any one of ⁇ 1> to ⁇ 5>, further including a benzodioxole compound.
- ⁇ 7> The photopolymerization initiator according to any one of ⁇ 1> to ⁇ 6> for dental materials.
- ⁇ 8> A photocurable composition containing the photopolymerization initiator according to any one of ⁇ 1> to ⁇ 7> and a polymerizable monomer.
- ⁇ 9> The photocurable composition according to ⁇ 8>, wherein the content ratio by mass of the photoradical generator to the total amount of the polymerizable monomer is 0.0001 to 1.0.
- ⁇ 10> The photocurable composition according to ⁇ 8> or ⁇ 9>, wherein the content ratio by mass of the photobase generator to the total amount of the polymerizable monomer is 0.0001 to 5.0.
- ⁇ 11> The photocurable composition according to any one of ⁇ 8> to ⁇ 10>, wherein the content ratio by mass of the peroxide to the total amount of the polymerizable monomer is 0.001 to 5.0. Stuff.
- ⁇ 12> The photocurable composition according to any one of ⁇ 8> to ⁇ 11>, further including a filler.
- ⁇ 13> The photocurable composition according to ⁇ 12>, wherein the filler includes a filler having a relative dielectric constant at 1 MHz and 25° C. of 8.0 or less.
- ⁇ 14> The photocurable composition according to ⁇ 12> or ⁇ 13>, in which the filler contains one or more fillers selected from the group consisting of silica, barium borosilicate glass, and aluminosilicate glass.
- ⁇ 15> The photocurable composition according to any one of ⁇ 8> to ⁇ 14> for dental materials.
- ⁇ 16> A cured product of the photocurable composition according to any one of ⁇ 8> to ⁇ 14>.
- ⁇ 17> A dental material comprising the cured product according to ⁇ 16>.
- a photopolymerization initiator capable of improving the polymerization depth of a photocurable composition, and a photocurable composition, a cured product and a dental material containing the photopolymerization initiator. ..
- the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
- the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified. means.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. ..
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- (meth)acryloyl means acryloyl or methacryloyl
- (meth)acrylate means acrylate or methacrylate.
- * in the chemical formula represents a bonding position.
- the photopolymerization initiator of the present disclosure contains a peroxide, a photobase generator, and a photoradical generator.
- a peroxide For example, when filling the composite resin to the deep position of the tooth and curing it, light irradiation is performed from the surface side of the tooth, so the composite resin existing at the deep position is polymerized compared to the composite resin existing on the surface. Is difficult to cure and is often difficult to cure.
- the photopolymerization initiator of the present disclosure contains a photobase generator, a peroxide, and a photoradical generator, thereby generating a large amount of radicals when the composite resin containing the photopolymerization initiator is irradiated with light.
- the photopolymerization initiator of the present disclosure includes a plurality of substances, it is referred to as a “photopolymerization initiator” or a “photopolymerization initiation composite material” for convenience.
- the photopolymerization initiator of the present disclosure contains a photoradical generator.
- the photopolymerization initiator of the present disclosure may include only one type of photoradical generator, or may include two or more types thereof.
- the photoradical generating agent in the present disclosure is a photoradical generating agent other than the peroxide described below.
- the photoradical generator in the photopolymerization initiator of the present disclosure is preferably a photoradical generator that is excited by light having a wavelength of 420 nm to 525 nm.
- the photopolymerization initiator of the present disclosure can be used as a photopolymerization initiator contained in a photocurable composition that is cured by light in the visible range (for example, a wavelength range of 420 nm to 525 nm) that has little effect on living organisms. It can be used more preferably. Specifically, it can be more suitably used as a medical photopolymerization initiator (particularly preferably a photopolymerization initiator for dental materials).
- Examples of the photoradical generator in the present disclosure include acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2'-phenylacetophenone, 2- Acetophenones such as aminoacetophenone, 4'-methylaminoacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl Benzoins such as 2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o -Benzoylbenzoate, 4-pheny
- the photoradical generator of the present disclosure is excited by light having a wavelength of 420 nm to 525 nm, and therefore, the Norrish type II photopolymerization initiator such as benzophenone, camphorquinone, indane, or a derivative thereof, or , Aniline compounds and iodonium salt compounds are preferred.
- the Norrish type II photopolymerization initiator such as benzophenone, camphorquinone, indane, or a derivative thereof, or , Aniline compounds and iodonium salt compounds are preferred.
- the Norrish II type photopolymerization initiator is a benzophenone or camphorquinone from the viewpoint of further improving the curing rate and the polymerization depth of the photocurable composition.
- Indane, and derivatives thereof are preferably contained, and more preferably camphorquinone.
- the photo radical generator in the present disclosure may contain an aniline compound and an iodonium salt compound.
- the photoradical generator in the present disclosure contains an aniline compound and an iodonium salt compound, it can be excited in the visible region. Moreover, the tint of the cured product of the photocurable composition can be suppressed.
- the photopolymerization initiator of the present disclosure may include a compound represented by the following formula (1) as an aniline compound.
- the photopolymerization initiator of the present disclosure may include only one type of compound represented by the following formula (1), or may include two or more types thereof.
- R 1 to R 7 each independently have one or more substituents selected from the group A consisting of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a halogen atom. It is a monovalent organic group having 1 to 50 carbon atoms or a hydrogen atom. However, at least two adjacent ones of R 1 to R 7 may be bonded to each other to form a ring.
- the monovalent organic group represented by R 1 to R 7 and having 1 to 50 carbon atoms includes a monovalent hydrocarbon group, a monovalent group containing a hetero atom and a carbon atom, and the like.
- the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkylaryl group, an alkenylaryl group, an alkynylaryl group, an arylalkyl group, an arylalkenyl group and an arylalkynyl group.
- the hetero atom in the monovalent group containing a hetero atom and a carbon atom include an oxygen atom, a sulfur atom and a nitrogen atom, and preferably at least one of the oxygen atom and the nitrogen atom.
- the monovalent organic group represented by R 1 to R 7 and having 1 to 50 carbon atoms preferably has 1 to 40 carbon atoms, and more preferably 1 to 30 carbon atoms.
- the monovalent organic group having 1 to 50 carbon atoms represented by R 1 to R 7 may have one or more substituents selected from the group A.
- Group A consists of oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups and halogen atoms.
- the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- the oxygen-containing group is not particularly limited, except that it is a group containing an oxygen atom.
- the oxygen-containing group may be a group composed of oxygen atoms (that is, an oxo group ( ⁇ O)).
- the oxygen-containing group preferably has 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and even more preferably 0 to 10 carbon atoms.
- an oxo group ( ⁇ O) a group represented by the following formula (A), a group represented by the following formula (B), a group represented by the following formula (C), a group represented by the following formula (D)
- A oxygen-containing group
- B a group represented by the following formula (B)
- C a group represented by the following formula (C)
- D a group represented by the following formula
- X 1A is a single bond or a divalent hydrocarbon group having 1 to 10 carbon atoms
- R 1A is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a carbon number. It is a monovalent organic group of 3 to 30, and * is a bonding position.
- X 1B is a single bond or a divalent organic group having 2 to 20 carbon atoms, and * is a bonding position.
- X 1C represents a single bond or a divalent organic group having 1 to 20 carbon atoms, and * represents a bonding position.
- X 1D represents a single bond or a monovalent organic group having 1 to 20 carbon atoms, and * represents a bonding position.
- the sulfur-containing group is not particularly limited except that it is a group containing a sulfur atom.
- the nitrogen-containing group is not particularly limited except that it is a group containing a nitrogen atom.
- the nitrogen-containing group may be a group composed of nitrogen atoms (that is, a nitrilo group ( ⁇ N)).
- examples of the nitrogen-containing group include nitrilo group ( ⁇ N), amino group (—NH 2 ), monoalkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, and the like.
- R 6 and R 7 are each independently an alkyl group having 1 to 4 carbon atoms, or R 6 and R 7 each have 2 to 8 carbon atoms formed by being bonded to each other. It is preferably an alkylene group (that is, a group for forming a nitrogen-containing heterocycle with a nitrogen atom).
- R 6 and R 7 are preferably each independently a methyl group or an ethyl group. In this case, more preferably, R 6 and R 7 are both methyl groups or both are ethyl groups.
- the molecular weight of the compound represented by formula (1) is not particularly limited and is 600 or less.
- the compound represented by the formula (1) is The present invention is not limited to this specific example.
- the photopolymerization initiator of the present disclosure may include only one type of these specific examples, or may include two or more types thereof.
- the photopolymerization initiator of the present disclosure may include a compound represented by the following formula (2) as an iodonium salt compound.
- X and Y may each independently have one or more substituents selected from the group A consisting of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group and a halogen atom, It is a monovalent hydrocarbon group having 6 to 50 carbon atoms and containing an aromatic ring, I + is an iodine cation, and Z ⁇ is an anion.
- the compound represented by formula (2), a cation represented by X-I + -Y, Z - is an anion and, a salt represented by.
- the one or more substituents selected from group A are the same as the one or more substituents selected from group A in formula (1).
- X and Y each independently represent an unsubstituted aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group.
- the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- the carbon numbers in X and Y are each independently preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12.
- Z ⁇ is an anion.
- anion represented by Z ⁇ there is no particular limitation on the type of anion represented by Z ⁇ , and examples thereof include PF 6 ⁇ , P(CF 3 ) 3 F 3 ⁇ , CF 3 SO 3 ⁇ , Cl ⁇ , CF 3 C 3 F 6 SO 3 ⁇ . , CH 3 C 6 H 4 SO 3 ⁇ , NO 3 ⁇ and the like.
- the molecular weight of the compound represented by the formula (2) is not particularly limited and may be, for example, 280 or more and 1000 or less.
- the photopolymerization initiator of the present disclosure contains a compound represented by the formula (2) in addition to the compound represented by the formula (1), it is represented by the formula (1) in the photopolymerization initiator of the present disclosure.
- the molar ratio of the compound represented by the formula (2) to the compound represented by the formula is, for example, preferably 0. .3 to 2.
- the sample A, the sample B, and the sample C have the same volume.
- the concentration of the compound represented by formula (1) in sample A and the concentration of the compound represented by formula (1) in sample B are adjusted to be the same value.
- the concentration of the compound represented by the formula (2) in the sample A and the concentration of the compound represented by the formula (2) in the sample C are adjusted to be the same value.
- an ultraviolet-visible (UV-Vis) absorption spectrum (hereinafter, also simply referred to as “spectrum”) is measured for each of the sample A, the sample B, and the sample C.
- the spectrum area of the sample A in the wavelength range of 350 nm to 550 nm is larger than the sum of the spectrum area of the sample B in the wavelength range of 350 nm to 550 nm and the spectrum area of the sample C in the wavelength range of 350 nm to 550 nm.
- it is larger it is determined that the photopolymerization initiator of the present disclosure forms a complex between the compound represented by Formula (1) and the compound represented by Formula (2).
- the complex of the compound represented by the formula (1) and the compound represented by the formula (2) includes a compound represented by the formula (1), a compound represented by the formula (2), and (if necessary. It can be formed by mixing) with other components.
- a compound represented by the formula (1) a compound represented by the formula (2)
- the above complex as a photopolymerization initiator can be formed.
- the temperature of each component during the above mixing is, for example, 20°C to 80°C.
- the mixing time is, for example, 10 minutes to 5 hours.
- a molar ratio of the compound represented by the formula (2) to the compound represented by the formula (1) when the above mixing is performed is not particularly limited, but is preferably 0.3 to 2.0, and more preferably 0.5 to 1.5.
- the content of the photoradical generator with respect to the total amount of the photopolymerization initiator of the present disclosure is preferably 0.0001% by mass to 1.0% by mass, more preferably 0.0001% by mass to 0.005% by mass, and 0.1. More preferably, it is 0002% by mass to 0.0008% by mass.
- the “total amount of photopolymerization initiator” means the total mass of the photoradical generator, the peroxide, the photobase generator, and the reducing agent as an optional component. The same applies to the above points.
- the content of the photoradical generator is, for example, in the range of 1.0% by mass to 99.0% by mass with respect to the total content of the peroxide, the photobase generator and the photoradical generator. Can be appropriately selected and used in consideration of the above content ratio [photoradical generator/polymerizable monomer] and the like.
- the photopolymerization initiator of the present disclosure may further contain a reducing agent.
- a reducing agent When the photopolymerization initiator of the present disclosure contains a reducing agent, it is possible to more efficiently generate radicals from the photoradical generator, particularly when the photopolymerization initiator is irradiated with visible light.
- the photopolymerization initiator of the present disclosure may include only one type of reducing agent, or may include two or more types of reducing agents. Examples of the reducing agent include amines and benzodioxole compounds.
- the photopolymerization initiator of the present disclosure is a benzodioxole compound (especially a benzodioxole having no nitrogen atom) as a reducing agent. It is preferable to further include a dioxole compound).
- a benzodioxole compound especially a benzodioxole having no nitrogen atom
- dioxole compound especially a benzodioxole having no nitrogen atom
- the photopolymerization initiator of the present disclosure contains a photoradical generator, but when the photoradical generator and the reducing agent are used in combination, the reducing agent and the peroxide contained in the photopolymerization initiator of the present disclosure react with each other. This may impair the stability of the photocurable composition containing the photopolymerization initiator of the present disclosure.
- a benzodioxole compound is selected as the reducing agent used in combination with the photoradical generator, the reactivity of the benzodioxole compound, which is the reducing agent, with the peroxide is low. The stability of the photocurable composition containing the polymerization initiator is maintained well.
- an amine, a benzodioxole compound containing a nitrogen atom, or the like is used as the reducing agent, it is possible to make them less likely to impair the stability by making them photo-latent.
- benzodioxole compound in the present disclosure examples include the following specific examples ((1-1) to (1-14)), but are not limited to these specific examples.
- the photoradical generator used in combination with the reducing agent from the viewpoint of the stability of the photocurable composition containing the photopolymerization initiator of the present disclosure, the above Norrish type II initiator is preferable, and camphorquinone is more preferable. ..
- a Norrish II type initiator and a benzodioxole compound are preferable, More preferred are camphorquinone and benzodioxole compounds.
- the photopolymerization initiator of the present disclosure uses a combination of a Norrish type II initiator and a benzodioxole compound as the photoradical generator and the reducing agent, it is visible from the near ultraviolet region as compared with each of these. It is more excellent in its activity to light in the region (in particular, the visible region having a wavelength of 420 nm to 525 nm). Therefore, when the photopolymerization initiator of the present disclosure uses a combination of the Norrish type II initiator and the benzodioxole compound as the photoradical generator and the reducing agent, the Norrish type II initiator and the benzodioxole compound are used.
- the curing rate and the polymerization depth of the photocurable composition can be further improved as compared with the case where each of the above is used alone.
- the photopolymerization initiator of the present disclosure uses a combination of a Norrish type II initiator and a benzodioxole compound as a photoradical generator and a reducing agent
- the photopolymerization initiator is cured by light in the near-ultraviolet region to the visible region. It is suitable as a photopolymerization initiator contained in the curable composition.
- the photopolymerization initiator of the present disclosure contains the above-mentioned combination as a photoradical generator and a reducing agent, the application is not particularly limited and can be applied to all applications in the industrial field, medical field, and the like.
- a photopolymerization initiator in a photocurable composition that is cured by light in the visible range (for example, the visible range of wavelength 420 nm to 525 nm) that has little effect on the living body, and more specifically, medical treatment Is particularly suitable as a photopolymerization initiator for use (particularly preferably a photopolymerization initiator for dental materials).
- the content ratio of the reducing agent to the photoradical generator (hereinafter, also referred to as the content mass ratio [reducing agent/photoradical generating agent]) is from the viewpoint of obtaining a good polymerization depth, and From the viewpoint of the reducing agent acting as a plasticizer and the elution of the photoradical generator from the cured product, 0.1 to 20.0 is preferable, 0.5 to 10.0 is more preferable, and 0.7 is preferable. It is more preferably to 1.5.
- the content of the reducing agent with respect to the total amount of the photopolymerization initiator of the present disclosure is preferably 0.0001% by mass to 1.0% by mass, more preferably 0.0002% by mass to 0.1% by mass, and 0.0003% by mass. % To 0.03 mass% is more preferable.
- the photopolymerization initiator of the present disclosure contains a photobase generator.
- the photobase generator is a compound that generates a base upon exposure to light, and can generate a curing reaction such as a polymerization reaction or a condensation reaction by using the generated base as a catalyst.
- Examples of the photobase generator that can be used include oxime ester compounds, acyl compounds, carbamate compounds, aminoacetophenone compounds, tertiary amine compounds, quaternary ammonium salt compounds and amide compounds.
- Specific examples include triazabicyclodecene/tetraphenyl boric acid, phosphazene base P1-t-octyl/tetraphenyl boric acid, triazabicyclodecene/oxoxanthenepropionic acid, formyldimethylbenzamide, piperidinecarbonylbenzoate and the like.
- the photopolymerization initiator of the present disclosure has a photobase generator having an oxime ester compound, an acyl compound, a carbamate compound, an aminoacetophenone compound, a tertiary amine compound, and a quaternary compound, because the cured product has an excellent curing depth. It is preferable that at least one selected from the group consisting of ammonium salt compounds and amide compounds is included, and it is more preferable that at least one selected from the group consisting of acyl compounds, tertiary amine compounds and quaternary ammonium salt compounds is included. preferable.
- the content mass ratio of the photobase generator to the total amount of the peroxide (hereinafter, also referred to as the content mass ratio [photobase generator/peroxide]) is from the viewpoint of obtaining a good polymerization depth.
- 01 to 10.0 is preferable, 0.3 to 3.0 is more preferable, and 0.5 to 2.3 is further preferable.
- the content of the photobase generator with respect to the total amount of the photopolymerization initiator of the present disclosure is preferably 0.001% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.1% by mass, and 0.1% by mass. It is more preferably from 01% by mass to 0.07% by mass.
- the photopolymerization initiator of the present disclosure contains a peroxide.
- radicals can also be generated from the peroxide, and a good polymerization depth can be obtained.
- peroxide in the present disclosure examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxide compounds such as m-toluoyl peroxide, t-butylperoxybenzoate, and bis-t-butylperoxide.
- Peroxy ester compounds such as oxyisophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate, t -Hydroperoxide compounds such as butyl hydroperoxide, alkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, 1,1-bis(t-butylperoxy)-3, Peroxyketal compounds such as 3,5-trimethylcyclohexane, ketone peroxide compounds such as methyl ethyl ketone peroxide, fluorine-containing peroxide compounds such as perfluoro(tert-butyl peroxide) and perfluorobenzoyl peroxide, potassium peroxide, hydrogen peroxide, etc.
- t -Hydroperoxide compounds such as buty
- the photopolymerization initiator of the present disclosure is a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a group consisting of an inorganic peroxide and an alkyl peroxide. It is preferable to contain at least one selected, and it is more preferable to contain at least one selected from the group consisting of diacyl peroxide compounds, hydroperoxide compounds, and inorganic peroxides.
- the content of the peroxide with respect to the total amount of the photopolymerization initiator of the present disclosure is preferably 0.001% by mass to 0.1% by mass, more preferably 0.005% by mass to 0.07% by mass, and 0.01 More preferably, it is from mass% to 0.05 mass %.
- the photocurable composition of the present disclosure contains the photopolymerization initiator of the present disclosure and a polymerizable monomer.
- the photopolymerization initiator in the photocurable composition of the present disclosure is the same as the photopolymerization initiator described above, and the preferable embodiments and the preferable ranges are the same as the photopolymerization initiator described above except the following.
- the total content of the photoradical generator, the peroxide, the photobase generator of the present disclosure, and the reducing agent as an optional component is, as described above, based on the polymerizable monomer. It may be appropriately selected in consideration of the content and the like, but may be, for example, in the range of 0.1% by mass to 10.0% by mass based on the total amount of the photocurable composition.
- the photocurable composition of the present disclosure contains a polymerizable monomer.
- the polymerizable monomer contained in the photocurable composition of the present disclosure may be only one kind or two or more kinds.
- a compound containing a radically polymerizable group is preferably used as the polymerizable monomer.
- the radically polymerizable group a group containing an ethylenic double bond is preferable, and a (meth)acryloyl group is particularly preferable.
- the polymerizable monomer preferably contains at least one (meth)acrylate compound.
- the proportion of the (meth)acrylate compound in the polymerizable monomer is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more.
- the proportion of the (meth)acrylate compound in the polymerizable monomer may be 100% by mass or less, 95% by mass or less, or 90% by mass or less.
- Examples of the (meth)acrylate compound include a monofunctional (meth)acrylate compound and a bifunctional or higher functional (meth)acrylate compound.
- the (meth)acrylate compound preferably contains a bifunctional or higher functional (meth)acrylate compound, more preferably a bifunctional to hexafunctional (meth)acrylate compound, and a bifunctional to tetrafunctional (meth)acrylate. It is more preferable to include a compound, and it is particularly preferable to include a bifunctional (meth)acrylate compound (that is, a di(meth)acrylate compound).
- bifunctional (meth)acrylate compound that is, di(meth)acrylate compound
- urethane di(meth)acrylate neopentyl di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, tricyclode Candimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tri Propylene glycol di(meth)acrylate, tetrapropylene glycol di
- the proportion of the di(meth)acrylate compound in the polymerizable monomer is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more.
- the proportion of the di(meth)acrylate compound in the polymerizable monomer may be 100% by mass or less, 95% by mass or less, or 90% by mass or less.
- the proportion of the di(meth)acrylate compound in the (meth)acrylate compound is preferably 60% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. Further, the proportion of the di(meth)acrylate compound in the (meth)acrylate compound may be 100% by mass or less, 95% by mass or less, or 90% by mass or less.
- JP-A-11-315059, JP-A-2001-70437, JP-A-2011-105722, JP-A-2000-204069, and JP-A-2013-544823 Reference may be made to the description of known documents such as International Publication No. 2016/125758 and International Publication No. 2015/119163.
- the content of the polymerizable monomer in the photocurable composition of the present disclosure is preferably 15% by mass or more, and more preferably 35% by mass or more, based on the total amount of the photocurable composition.
- the content of the polymerizable monomer in the photocurable composition is preferably 70% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the content of the photo radical generator contained in the photo-curable composition of the present disclosure is preferably 0.0001 to 1.0, more preferably 0.0005 to 0.1, and 0.0005 to 0.01 It is more preferable that there is.
- the content mass ratio of the photobase generator to the total amount of the polymerizable monomer (hereinafter, also referred to as content mass ratio [photobase generator/polymerizable monomer]) is 0.0001 to 5.0. Is preferable, 0.001 to 1.0 is more preferable, and 0.005 to 0.1 is further preferable.
- the content ratio of the content of the peroxide to the total amount of the polymerizable monomer is preferably 0.001 to 5.0. , 0.003 to 1.0 is more preferable, and 0.003 to 0.05 is further preferable.
- the photocurable composition of this indication may contain a filler as needed.
- a filler a general filler used in the dental field can be used. Fillers are generally roughly classified into organic fillers and inorganic fillers.
- organic filler examples include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, crosslinked polymethylmethacrylate, crosslinked polyethylmethacrylate, ethylene-vinylacetate copolymer, Examples thereof include fine powders of styrene-butadiene copolymer and the like.
- various glasses various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, Examples thereof include fine powders of titanium dioxide and hydroxyapatite, silica, alumina, zirconia, titania and the like.
- the above-mentioned various glasses have silicon dioxide as a main component, and may contain oxides of heavy metals, boron, aluminum, etc., if necessary.
- various glasses include barium borosilicate glass, aluminosilicate glass (boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, etc.) and the like.
- an inorganic filler examples include, for example, barium borosilicate glass (Kimble Raysorb T3000, shot 8235, shot GM27984, shot GM39923, etc.), strontium boroaluminosilicate glass (Raysorb T4000, shot G018-093, shot GM32087). Etc.), lanthanum glass (Shot GM31684 etc.), fluoroaluminosilicate glass (Shot G018-091, Shot G018-117 etc.), boroaluminosilicate glass containing zirconium, cesium and the like (Shot G018-307, G018-308, G018-). 310 etc.).
- an organic-inorganic composite filler obtained by previously adding a polymerizable monomer to an inorganic filler to form a paste, polymerizing and curing, and pulverizing may be used.
- an embodiment containing a microfiller having a particle size of 0.1 ⁇ m or less is one of the preferred embodiments as the photocurable composition for dental materials.
- the material of the filler having such a small particle diameter silica (for example, trade name Aerosil), alumina, zirconia, titania and the like are preferable.
- the filler preferably contains at least one filler selected from the group consisting of silica, barium borosilicate glass, and aluminosilicate glass.
- these fillers may be surface-treated with a surface treatment agent such as a silane coupling agent.
- a surface treatment agent such as a silane coupling agent.
- known silane coupling agents such as methacryloxyalkyltrimethoxysilane (carbon number between methacryloxy group and silicon atom: 3 to 12), methacryloxyalkyltriethoxysilane (methacryloxy group) And carbon atoms between 3 and 12), and organic silicon compounds such as vinyltrimethoxysilane, vinylethoxysilane, and vinyltriacetoxysilane.
- the content of the filler in the photocurable composition of the present disclosure is preferably 30% by mass or more, more preferably 40% by mass or more, relative to the total amount of the photocurable composition. It is more preferably 50% by mass or more.
- the content of the filler in the photocurable composition is preferably 80% by mass or less, more preferably 75% by mass or less, and 65% by mass or less. More preferable.
- the photocurable composition of the present disclosure preferably further contains a filler (hereinafter, also referred to as a specific filler) having a relative dielectric constant ( ⁇ S ) of 8.0 or less at 1 MHz and 25° C.
- a filler hereinafter, also referred to as a specific filler
- the specific dielectric constant ( ⁇ S ) of the specific filler at 1 MHz and 25° C. is more preferably 6.5 or less.
- the lower limit of the relative dielectric constant ( ⁇ S ) of the specific filler at 1 MHz and 25° C. is not particularly limited and may be 0.1 or more, or 1.0 or more.
- Examples of the filler having a relative dielectric constant ( ⁇ S ) at 1 MHz and 25° C. of 8.0 or less include silica, barium borosilicate glass, aluminosilicate glass (boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate). Such as glass).
- the relative permittivity ( ⁇ S ) in the present disclosure is measured under the condition of 25° C. and 1 MHz based on the IPC standard test manual IPC-TM-650, paragraph 2.5.5.9.
- an impedance material analyzer HP4291A can be used as the measuring device.
- the relative permittivity of the filler means the relative permittivity of a component (also referred to as a filler component in the present specification) contained in the photocurable composition as the filler.
- a component contained in the photocurable composition as a filler is a target of measurement of the relative dielectric constant for the purpose of eliminating the influence of voids or the like in the formed filler.
- the measurement sample does not necessarily have to have the filler shape as long as it is made of the same substance as the filler to be measured.
- Specific examples of the component contained in the photocurable composition as the filler include the above-mentioned organic fillers and inorganic fillers.
- the total content of the specific filler with respect to the total amount of the filler is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.
- the photocurable composition of the present disclosure may include a photosensitizer.
- the photosensitizer means a component that facilitates generation of radicals by the photoradical generator by propagating energy obtained by absorbing light itself to the photoradical generator.
- Examples of the photosensitizer in the present disclosure include naphthalene compounds such as diethoxynaphthalene, anthracene compounds such as dibutoxyanthracene, thioxanthone compounds such as isopropylthioxanthone, carbonylbis(diethylaminocoumarin), benzimidazoyldimethylaminocoumarin and the like.
- Examples include coumarin compounds. Among them, naphthalene compounds, anthracene compounds, thioxanthone compounds and coumarin compounds are preferable from the viewpoint of improving the polymerization depth.
- the content mass ratio of the photosensitizer to the total amount of the polymerizable monomer (hereinafter, also referred to as the content mass ratio [photosensitizer/polymerizable monomer]) is from the viewpoint of obtaining a good polymerization depth. Therefore, 0.0003 to 0.07 is preferable, 0.0005 to 0.05 is more preferable, and 0.001 to 0.035 is further preferable.
- the photocurable composition of the present disclosure may contain other components than the components described above, if necessary.
- Other components include a polymerization inhibitor, a colorant (eg pigment or dye), a reinforcing material (eg fiber), a bactericide, a disinfectant, a stabilizer and a preservative.
- a polymerization inhibitor e.g pigment or dye
- a reinforcing material e.g fiber
- a bactericide e.g., bactericide, a disinfectant, a stabilizer
- a cured product obtained by curing the photocurable composition can be obtained.
- the photocurable composition of the present disclosure may be subjected to heat treatment after light irradiation to improve the mechanical properties of the cured product.
- the use of the photopolymerization initiator and the photocurable composition of the present disclosure is not particularly limited.
- the photopolymerization initiator and photocurable composition of the present disclosure can be used, for example, as a paint, a composition for forming a coating film, a dental material, a component in a dental material, and the like.
- the photopolymerization initiator and the photocurable composition of the present disclosure are preferably used as a dental material or a component in a dental material. That is, the photopolymerization initiator of the present disclosure is preferably a photopolymerization initiator for dental materials, and the photocurable composition of the present disclosure is preferably a photocurable composition for dental materials.
- the cured product of the present disclosure is a cured product of the photocurable composition of the present disclosure described above or the dental material of the present disclosure described above. Therefore, the cured product of the present disclosure has an excellent polymerization depth.
- the cured product of the present disclosure is obtained by subjecting the above-described photocurable composition of the present disclosure or the above-described dental material of the present disclosure to light irradiation (preferably visible light irradiation). After the light irradiation, a heat treatment may be further performed to improve the mechanical properties of the cured product.
- the dental material of the present disclosure comprises a cured product of the photocurable composition of the present disclosure described above.
- the dental material of the present disclosure is a cured product having an excellent polymerization depth.
- the dental material of the present disclosure comprises the above cured product. As a result, it is possible to perform a dental restoration having an excellent polymerization depth.
- Examples of the dental material composition and dental material of the present disclosure include a dental restoration composite resin, a denture base resin, a denture base lining material, an impression material, and an attachment material (resin cement, resin-added glass ionomer cement). Etc.), dental adhesives (orthodontic adhesives, cavity application adhesives, etc.), tooth cleft sealing materials, CAD/CAM resin blocks, temporary crowns, artificial tooth materials and the like.
- the composite resin for dental restoration include a composite resin for dental crown, a composite resin for filling a caries cavity, a composite resin for building an abutment, and a composite resin for filling and restoration.
- a dental restorative composite resin is particularly preferable. As described above, by curing the dental material composition of the present disclosure, a cured product having an excellent polymerization depth can be obtained. Therefore, when the composition for dental materials and the dental material of the present disclosure are composite resins for dental restoration, dental restoration excellent in polymerization depth can be performed. That is, excellent curing performance (particularly, curing performance against irradiation with light in the visible region) is exhibited from the surface to the deep part of the composite resin for dental restoration filled with tooth defects and the like.
- UDMA Dimethacryloxyethyl trimethylhexyl dicarbamate (urethane dimethacrylate)
- TEGDMA Triethylene glycol dimethacrylate
- Photobase generator The following were prepared as photobase generators.
- TBD/BPh 4 triazabicyclodecene/tetraphenylborate
- PN/BPh 4 phosphazene base
- O0396 triazabicyclodecene/oxoxanthenepropionate
- FDB formyldimethylbenzamide
- PCB Piperidine carbonyl benzoate
- CQ camphorquinone (Norish type II initiator, which is a photoradical generator excited by light having a wavelength of 400 nm to 500 nm)
- ⁇ Filler> The following were prepared as a filler. Filler: Barium borosilicate glass (0.85 ⁇ m, treated with silane coupling, 1 MHz, relative dielectric constant ( ⁇ S ) at 25° C.: 6.2) The relative permittivity was measured by the above method.
- Examples 1 to 14 and Comparative Examples 1 to 5 ⁇ Preparation of photocurable composition> Each component shown in the following Table 1 was weighed in a light-shielding bottle, and then stirred for 2 minutes under the conditions of 20 kPa and 2000 rpm (revolutions per minute) using a spinning revolution mixer manufactured by THINKY, and Examples 1 to 14 and Comparative Photocurable compositions of Examples 1 to 5 were obtained.
- the number in each component column shown in Table 1 means the amount (part by mass) of each component.
- the blank in Table 1 means that the component was not used.
- A The polymerization depth was 40 mm or more.
- B The polymerization depth was less than 40 mm and 35 mm or more.
- C The polymerization depth was less than 35 mm and 30 mm or more.
- D The polymerization depth was less than 30 mm and 25 mm or more.
- E The polymerization depth was less than 25 mm.
- Examples 1 to 14 were excellent in the depth of polymerization. Among them, Examples 4 and 5 using the coumarin derivative as the photosensitizer, and Examples 6, 8 and 11 using the anthracene derivative and the naphthalene derivative together were excellent in the polymerization depth. On the other hand, although not shown in Table 1, in Examples 6, 8 and 11 in which the anthracene derivative and the naphthalene derivative were used in combination, coloring of the cured product was suppressed as compared with Examples 4 and 5 in which the coumarin derivative was used. .. Furthermore, Examples 1 to 11 using benzodioxole or its derivative without using amine as the reducing agent were superior in stability to Example 12 using amine as the reducing agent.
- Example 10 using hydroperoxide as the peroxide was excellent in the polymerization depth.
- Comparative Example 1 containing no photoradical generator, Comparative Example 2 containing no photobase generator and peroxide, Comparative Example 3 containing no peroxide, Comparative Example 4 containing no photobase generator and Comparative Example 5 had a poor polymerization depth.
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Abstract
Description
<1> 過酸化物と、光塩基発生剤と、光ラジカル発生剤と、を含む光重合開始剤。
<2> 前記光ラジカル発生剤が、波長420nm~525nmのいずれかの光で励起される<1>に記載の光重合開始剤。
<3> 前記光ラジカル発生剤が、ノリッシュII型開始剤、又は、アニリン化合物及びヨードニウム塩化合物である<1>又は<2>に記載の光重合開始剤。
<4> 前記過酸化物が、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、無機過酸化物及びアルキル過酸化物からなる群より選択される少なくとも1つを含む<1>~<3>のいずれか1つに記載の光重合開始剤。
<5> 前記光塩基発生剤が、オキシムエステル化合物、アシル化合物、カルバメート化合物、アミノアセトフェノン化合物、3級アミン化合物、4級アンモニウム塩化合物及びアミド化合物からなる群より選択される少なくとも1つを含む<1>~<4>のいずれか1つに記載の光重合開始剤。
<6> ベンゾジオキソール化合物をさらに含む<1>~<5>のいずれか1つに記載の光重合開始剤。
<7> 歯科材料用の<1>~<6>のいずれか1つに記載の光重合開始剤。
<8> <1>~<7>のいずれか1つに記載の光重合開始剤と、重合性単量体と、を含む光硬化性組成物。
<9> 前記重合性単量体の全量に対する前記光ラジカル発生剤の含有質量比が、0.0001~1.0である<8>に記載の光硬化性組成物。
<10> 前記重合性単量体の全量に対する前記光塩基発生剤の含有質量比が、0.0001~5.0である<8>又は<9>に記載の光硬化性組成物。
<11> 前記重合性単量体の全量に対する前記過酸化物の含有質量比が、0.001~5.0である<8>~<10>のいずれか1つに記載の光硬化性組成物。
<12> フィラーをさらに含む<8>~<11>のいずれか1つに記載の光硬化性組成物。
<13> 前記フィラーが、1MHz、25℃における比誘電率が8.0以下であるフィラーを含む<12>に記載の光硬化性組成物。
<14> 前記フィラーが、シリカ、バリウムボロシリケートガラス、及びアルミノシリケートガラスからなる群から選択される1つ以上のフィラーを含む<12>又は<13>に記載の光硬化性組成物。
<15> 歯科材料用の<8>~<14>のいずれか1つに記載の光硬化性組成物。
<16> <8>~<14>のいずれか1つに記載の光硬化性組成物の硬化物。
<17> <16>に記載の硬化物からなる歯科材料。
本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において、「(メタ)アクリロイル」とは、アクリロイル又はメタクリロイルを意味し、「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。
本開示において、化学式中の*は、結合位置を表す。
本開示の光重合開始剤は、過酸化物と、光塩基発生剤と、光ラジカル発生剤と、を含む。
例えば歯牙の深い位置までコンポジットレジンを充填して硬化させようとする場合、光の照射は歯牙の表面側から行うため、表面に存在するコンポジットレジンと比較して深い位置に存在するコンポジットレジンは重合が進みにくく、硬化させることが困難である場合が多い。
本開示の光重合開始剤は、光塩基発生剤と、過酸化物と、光ラジカル発生剤と、を含むことで、光重合開始剤を含むコンポジットレジンに光を照射した際に多量のラジカルを発生させることができるため、例えば歯牙の深い位置においても良好にコンポジットレジン中に含まれる重合性単量体の重合を進行させることができる。
本開示の光重合開始剤は複数の物質を含むが、便宜的に「光重合開始剤」又は「光重合開始複合材」と称する。
本開示の光重合開始剤は、光ラジカル発生剤を含む。
本開示の光重合開始剤は、光ラジカル発生剤を、1種のみ備えていてもよいし、2種以上備えていてもよい。
なお、本開示における光ラジカル発生剤は、後述の過酸化物以外の光ラジカル発生剤である。
これによって、本開示の光重合開始剤を、特に生体への影響が少ない可視領域(例えば、波長420nm~525nmの領域)の光によって硬化する光硬化性組成物に含まれる光重合開始剤として、より好適に用いることができる。具体的には、医療用光重合開始剤(特に好ましくは歯科材料用光重合開始剤)としてより好適に用いることができる。
本開示の光ラジカル発生剤としてノリッシュII型光重合開始剤を用いる場合、ノリッシュII型光重合開始剤は、光硬化性組成物の硬化速度及び重合深度をより向上させる観点から、ベンゾフェノン、カンファーキノン、インダン、及びこれらの誘導体からなる群から選択される1つ以上を含むことが好ましく、カンファーキノンを含むことがより好ましい。
本開示における光ラジカル発生剤として、アニリン化合物及びヨードニウム塩化合物を含んでいてもよい。
本開示における光ラジカル発生剤がアニリン化合物及びヨードニウム塩化合物を含むことで、可視領域で励起することができる。また、光硬化性組成物の硬化物の色味を抑制することができる。
本開示の光重合開始剤は、アニリン化合物として、下記式(1)で表される化合物を含んでいてもよい。
本開示の光重合開始剤は、下記式(1)で表される化合物を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。
1価の炭化水素基としては、アルキル基、アルケニル基、アルキニル基、アリール基、アルキルアリール基、アルケニルアリール基、アルキニルアリール基、アリールアルキル基、アリールアルケニル基、アリールアルキニル基、等が挙げられる。
ヘテロ原子及び炭素原子を含む1価の基におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられ、好ましくは酸素原子及び窒素原子の少なくとも一方である。
群Aは、酸素含有基、硫黄含有基、窒素含有基及びハロゲン原子からなる。
群Aにおいて、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子又はヨウ素原子が好ましい。
酸素含有基は、酸素原子からなる基(即ち、オキソ基(=O))であってもよい。
酸素含有基の炭素数は、0~30が好ましく、0~20がより好ましく、0~10がより好ましい。
酸素含有基としては、オキソ基(=O)、下記式(A)で表される基、下記式(B)で表される基、下記式(C)で表される基、下記式(D)で表される基、等が挙げられる。
式(B)中、X1Bは、単結合又は炭素数2~20の2価の有機基であり、*は、結合位置である。
式(C)中、X1Cは、単結合又は炭素数1~20の2価の有機基であり、*は、結合位置である。
式(D)中、X1Dは、単結合又は炭素数1~20の1価の有機基であり、*は、結合位置である。
硫黄含有基としては、例えば、チオール基(-SH)、チオキソ基(=S)等が挙げられる。
窒素含有基としては、例えば、ニトリロ基(≡N)、アミノ基(-NH2)、炭素数1~10のモノアルキルアミノ基、炭素数2~20のジアルキルアミノ基等が挙げられる。
本開示の光重合開始剤は、これらの具体例を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。
本開示の光重合開始剤は、ヨードニウム塩化合物として、下記式(2)で表される化合物を含んでいてもよい。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子又はヨウ素原子が好ましい。
X及びYにおける炭素数は、それぞれ独立に、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。
Z-で表されるアニオンの種類には特に制限はなく、例えば、PF6 -、P(CF3)3F3 -、CF3SO3 -、Cl―、CF3C3F6SO3 -、CH3C6H4SO3 -、NO3 -等が挙げられる。
本開示の光重合開始剤は、これらの具体例を、1種のみ含んでいてもよいし、2種以上含んでいてもよい。
本開示の光重合開始剤において、光ラジカル発生剤としてアニリン化合物及びヨードニウム塩化合物を用いる場合には、式(1)で表される化合物と式(2)で表される化合物との錯体が形成されていることが好ましい。
まず、式(1)で表される化合物、式(2)で表される化合物、及びトリエチレングリコールジメタクリレート(TEGDMA)からなるサンプルAと、
式(1)で表される化合物及びTEGDMAからなるサンプルBと、
式(2)で表される化合物及びTEGDMAからなるサンプルCと、
のそれぞれを準備する。
ここで、サンプルA、サンプルB、及びサンプルCは、同体積とする。
また、サンプルA中の式(1)で表される化合物の濃度と、サンプルB中の式(1)で表される化合物の濃度と、が同じ値となるように調整する。
また、サンプルA中の式(2)で表される化合物の濃度と、サンプルC中の式(2)で表される化合物の濃度と、が同じ値となるように調整する。
次に、サンプルA、サンプルB、及びサンプルCのそれぞれについて、紫外可視(UV-Vis)吸収スペクトル(以下、単に「スペクトル」ともいう)を測定する。
サンプルAの350nm~550nmの波長範囲でのスペクトルの面積が、サンプルBの350nm~550nmの波長範囲でのスペクトルの面積とサンプルCの350nm~550nmの波長範囲でのスペクトルの面積との合計よりも大きい場合、本開示の光重合開始剤において、式(1)で表される化合物と式(2)で表される化合物との錯体が形成されていると判断する。
上記混合を行う時間は、例えば、10分~5時間である。
なお、上記「光重合開始剤の全量」は、光ラジカル発生剤と過酸化物と光塩基発生剤と任意成分としての還元剤と、の全質量を意味する。上記の点については、以下においても同様である。
本開示の光重合開始剤は、還元剤をさらに含んでいてもよい。
本開示の光重合開始剤が還元剤を含むことで、特に可視光を光重合開始剤に照射した場合に、光ラジカル発生剤からラジカルをより効率よく発生させることができる。
また、本開示の光重合開始剤は、還元剤を1種のみ備えていてもよいし、2種以上備えていてもよい。
還元剤としては、アミン、ベンゾジオキソール化合物等が挙げられる。
還元剤としてベンゾジオキソール化合物を用いる場合に光重合開始剤を含む光硬化性組成物の安定性を向上させることができる理由は以下のように推測される。
本開示の光重合開始剤は、光ラジカル発生剤を含むが、光ラジカル発生剤と還元剤を併用する場合に、還元剤と本開示の光重合開始剤に含まれる過酸化物とが反応することで、本開示の光重合開始剤を含む光硬化性組成物の安定性を損なう場合がある。
しかし、光ラジカル発生剤と併用する還元剤としてベンゾジオキソール化合物を選択する場合には、還元剤であるベンゾジオキソール化合物と過酸化物とは反応性が低いために、本開示の光重合開始剤を含む光硬化性組成物の安定性が良好に保持される。
一方、還元剤として、アミン、窒素原子を含むベンゾジオキソール化合物等を用いる場合に、これらを光潜在化することで、安定性を損ないにくくして使用することが可能である。
また、光ラジカル発生剤と還元剤との組合せとしては、本開示の光重合開始剤を含む光硬化性組成物の安定性の観点から、ノリッシュII型開始剤及びベンゾジオキソール化合物が好ましく、カンファーキノン及びベンゾジオキソール化合物がより好ましい。
従って、本開示の光重合開始剤が、光ラジカル発生剤及び還元剤として、ノリッシュII型開始剤及びベンゾジオキソール化合物の組み合わせを用いる場合には、ノリッシュII型開始剤及びベンゾジオキソール化合物の各々を単独で用いた場合と比較して、光硬化性組成物の硬化速度及び重合深度をより向上させることができる。
本開示の光重合開始剤が、光ラジカル発生剤及び還元剤として上記の組合せを含む場合、用途には特に制限はなく、工業分野、医療分野等におけるあらゆる用途に適用できる。中でも、特に、生体への影響が少ない可視領域(例えば、波長420nm~525nmの可視領域)の光によって硬化する光硬化性組成物における光重合開始剤として好適であり、より具体的には、医療用光重合開始剤(特に好ましくは歯科材料用光重合開始剤)として特に好適である。
本開示の光重合開始剤は、光塩基発生剤を含む。
光塩基発生剤は、露光により塩基を発生する化合物であり、発生した塩基を触媒として、重合反応、縮合反応等の硬化反応を発生させることができる。
上記の中でも、硬化物の硬化深度が優れることから、本開示の光重合開始剤は、光塩基発生剤が、オキシムエステル化合物、アシル化合物、カルバメート化合物、アミノアセトフェノン化合物、3級アミン化合物、4級アンモニウム塩化合物及びアミド化合物からなる群より選択される少なくとも1つを含むことが好ましく、アシル化合物、3級アミン化合物及び4級アンモニウム塩化合物からなる群より選択される少なくとも1つを含むことがより好ましい。
本開示の光重合開始剤は、過酸化物を含む。
これによって、上述の光ラジカル発生剤から発生するラジカルに加えて、さらに過酸化物からもラジカルを発生させることができ、良好な重合深度を得ることができる。
良好な重合深度を得る観点から、上記の中でも、本開示の光重合開始剤は、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、無機過酸化物及びアルキル過酸化物からなる群より選択される少なくとも1つを含むことが好ましく、ジアシルパーオキサイド化合物、ハイドロパーオキサイド化合物及び無機過酸化物からなる群より選択される少なくとも1つを含むことがより好ましい。
本開示の光硬化性組成物は、本開示の光重合開始剤と、重合性単量体と、を含む。
本開示の光硬化性組成物における光重合開始剤は既述の光重合開始剤と同様であり、好ましい態様及び好ましい範囲については、下記以外は既述の光重合開始剤と同様である。
本開示の光硬化性組成物は、重合性単量体を含有する。
本開示の光硬化性組成物に含有される重合性単量体は、1種のみであってもよいし2種以上であってもよい。
ラジカル重合性基としては、エチレン性二重結合を含む基が好ましく、(メタ)アクリロイル基が特に好ましい。
この場合、重合性単量体中に占める(メタ)アクリレート化合物の割合は、60質量%以上が好ましく、80質量%以上がより好ましく、90質量%以上が更に好ましい。
また、重合性単量体中に占める(メタ)アクリレート化合物の割合は、100質量%以下としてもよく、95質量%以下としてもよく、90質量%以下としてもよい。
(メタ)アクリレート化合物は、二官能以上の(メタ)アクリレート化合物を含むことが好ましく、二官能~六官能の(メタ)アクリレート化合物を含むことがより好ましく、二官能~四官能の(メタ)アクリレート化合物を含むことが更に好ましく、二官能の(メタ)アクリレート化合物(即ち、ジ(メタ)アクリレート化合物)を含むことが特に好ましい。
また、重合性単量体中に占めるジ(メタ)アクリレート化合物の割合は、100質量%以下としてもよく、95質量%以下としてもよく、90質量%以下としてもよい。
また、(メタ)アクリレート化合物中に占めるジ(メタ)アクリレート化合物の割合は、100質量%以下としてもよく、95質量%以下としてもよく、90質量%以下としてもよい。
また、光硬化性組成物中における重合性単量体の含有量は、70質量%以下が好ましく、45質量%以下がより好ましく、40質量%以下がさらに好ましい。
本開示の光硬化性組成物は、必要に応じ、フィラーを含有してもよい。
フィラーとしては、歯科分野で用いられる一般的なフィラーを使用することができる。 フィラーは、通常、有機フィラーと無機フィラーとに大別される。
上記各種ガラス類は、二酸化珪素を主成分とし、必要に応じて重金属、ホウ素、アルミニウム等の酸化物を含有してもよい。
各種ガラス類としては、例えば、バリウムボロシリケートガラス、アルミノシリケートガラス(ボロアルミノシリケートガラス、ストロンチウムボロアルミノシリケートガラス、フルオロアルミノシリケートガラスなど)等が挙げられる。
かかる粒径の小さなフィラーの材質としては、シリカ(例えば、商品名アエロジル)、アルミナ、ジルコニア、チタニア等が好ましい。
上記の中でも、フィラーとしては、シリカ、バリウムボロシリケートガラス、及びアルミノシリケートガラスからなる群から選択される1つ以上のフィラーを含むことが好ましい。
また、硬化物の靭性低下及び組成物の粘度抑制の観点から、光硬化性組成物中におけるフィラーの含有量は、80質量%以下が好ましく、75質量%以下がより好ましく、65質量%以下がさらに好ましい。
特定フィラーの1MHz、25℃における比誘電率(εS)としては、6.5以下であることがより好ましい。
特定フィラーの1MHz、25℃における比誘電率(εS)の下限については、特に制限はなく、0.1以上であってもよく、1.0以上であってもよい。
測定装置としては、例えば、インピダンスマテリアルアナライザーHP4291Aを用いることができる。
フィラー成分を用いてフィラーを形成し、形成されたフィラーに対して比誘電率を測定する場合、形成されたフィラーにおける空隙等の影響から比誘電率の値が低く測定される場合がある。
本開示におけるフィラーの比誘電率は、形成されたフィラーにおける空隙等の影響を排除することを目的として、フィラーとして光硬化性組成物中に含まれる成分を比誘電率の測定対象とする。このため、測定サンプルは、測定対象のフィラーと同じ物質から構成されていれば、必ずしもフィラー形状でなくてもよい。
フィラーとして光硬化性組成物中に含まれる成分の具体例としては、例えば、上述の有機フィラー、無機フィラー等が挙げられる。
本開示の光硬化性組成物は、光増感剤を含んでいてもよい。
本開示において光増感剤とは、自らが光を吸収して得たエネルギーを上記光ラジカル発生剤に伝搬させることで、光ラジカル発生剤によるラジカルの発生を容易にする成分を意味する。
上記の中でも、重合深度を良好とする観点から、ナフタレン化合物、アントラセン化合物、チオキサントン化合物及びクマリン化合物が好ましい。
本開示の光硬化性組成物は、必要に応じ、上述した成分以外のその他の成分を含有してもよい。
その他の成分としては、重合禁止剤、着色剤(例えば、顔料又は染料)、補強材(例えばファイバー)、殺菌剤、消毒剤、安定化剤、保存剤等が挙げられる。
その他の成分についても、例えば、特開平11-315059号公報、特開2001-70437号公報、特開2011-105722号公報、特開2000-204069号公報、特表2013-544823号公報、国際公開第2016/125758号、国際公開第2015/119163号等の公知文献の記載を適宜参照してもよい。
本開示の光硬化性組成物に対し、光照射の後、更に熱処理を施すことにより、硬化物の機械的物性を向上させてもよい。
本開示の光重合開始剤及び光硬化性組成物の用途には特に制限はない。
本開示の光重合開始剤及び光硬化性組成物は、例えば、塗料、コーティング膜形成用組成物、歯科材料、歯科材料中の成分等として用いることができる。
本開示の光重合開始剤及び光硬化性組成物は、歯科材料として、又は、歯科材料中の成分として用いられることが好ましい。即ち、本開示の光重合開始剤は歯科材料用の光重合開始剤であることが好ましく、本開示の光硬化性組成物は歯科材料用の光硬化性組成物であることが好ましい。
本開示の硬化物は、上述した本開示の光硬化性組成物又は上述した本開示の歯科材料の硬化物である。
従って、本開示の硬化物は、重合深度に優れている。
本開示の硬化物は、上述した本開示の光硬化性組成物又は上述した本開示の歯科材料に対し、光照射(好ましくは可視光の照射)を施すことによって得られる。
上記光照射の後、更に熱処理を施すことにより、硬化物の機械的物性を向上させてもよい。
本開示の歯科材料は、上述した本開示の光硬化性組成物の硬化物からなる。
本開示の歯科材料は、重合深度に優れた硬化物である。
本開示の歯科材料は上記硬化物からなる。これによって、重合深度に優れた歯科修復を行うことができる。
歯科修復用コンポジットレジンとしては、歯冠用コンポジットレジン、齲蝕窩洞充填用コンポジットレジン、支台築造用コンポジットレジン、充填修復用コンポジットレジン等が挙げられる。
前述したとおり、本開示の歯科材料用組成物を硬化させることにより、重合深度に優れた硬化物が得られる。
従って、本開示の歯科材料用組成物及び歯科材料が歯科修復用コンポジットレジンである場合には、重合深度に優れた歯科修復を行うことができる。即ち、歯の欠陥等に充填された歯科修復用コンポジットレジンの表面から深部にわたり、優れた硬化性能(特に、可視領域の光の照射に対する硬化性能)が発揮される。
重合性単量体として、以下のものを準備した。
UDMA:ジメタクリロキシエチルトリメチルヘキシルジカルバメート(ウレタンジメタクリレート)
TEGDMA:トリエチレングリコールジメタクリレート
光増感剤として、以下のものを準備した。
ITX:イソプロピルチオキサントン
UVS-1331:ジブトキシアントラセン
UVS-2171:ジエトキシナフタレン
KCD:カルボニルビス(ジエチルアミノクマリン)
C7:ベンジミダゾイルジメチルアミノクマリン
過酸化物として、以下のものを準備した。
BPO:ベンゾイルパーオキサイド
POSNH4:アンモニウムパーオキソジスルフェート
CHP:クミンハイドロパーオキサイド
光塩基発生剤として、以下のものを準備した。
TBD・BPh4:トリアザビシクロデセン・テトラフェニルホウ酸
PN・BPh4:フォスファゼン塩基P1-t-オクチル・テトラフェニルホウ酸
O0396:トリアザビシクロデセン・オキソクサンテンプロピオン酸
FDB:ホルミルジメチルベンザミド
PCB:ピペリジンカルボニルベンゾエート
光ラジカル発生剤として、以下のものを準備した。
CQ:カンファーキノン(ノリッシュII型開始剤、波長400nm~500nmの光で励起される光ラジカル発生剤である。)
BDO:ベンゾジオキソール
PB:ピペロニルブトキシド
EDB:エチルジメチルアミノベンゾエート
フィラーとして、以下のものを準備した。
フィラー:バリウムボロシリケートガラス(0.85μm、シランカップリング処理済、1MHz、25℃における比誘電率(εS):6.2)
上記比誘電率は、上述の方法により測定した。
<光硬化性組成物の調製>
遮光瓶に下記表1に示す各成分を秤量し、次いで、THINKY社製自転公転ミキサーを用い、20kPa、2000rpm(revolutions per minute)の条件で2分間撹拌し、実施例1~実施例14及び比較例1~比較例5の光硬化性組成物を得た。
表1に示す各成分欄の数字は、各成分の量(質量部)を意味する。
表1中の空欄は、その成分を用いなかったことを意味する。
実施例1~実施例14及び比較例1~比較例5の光硬化性組成物について、それぞれ、以下のようにして安定性の評価を行った。
遮光瓶に光硬化組成物を入れ、24時間後、容器内の組成物をスパチュラで撹拌し、流動性のないゲル状の硬化物が見られるかを調べた。結果を表1に示す。
下記評価基準において、安定性に最も優れる評点は「A」である。
A:流動性が良好であり、ゲル状の硬化物は全く見られなかった。
B:流動性があり、光硬化組成物の全体積におけるおよそ半分にゲル状の硬化物が見られた。
実施例1~実施例14及び比較例1~比較例5の光硬化性組成物について、それぞれ、以下のようにして重合深度の評価を行った。
10mm×75mmのガラスチューブに光硬化組成物を入れ、Kulzer製Translux2wave光照射装置を用い、20秒間照射した。その後遮光下に96時間静置し、ガラスチューブから取り出した硬化物の長さを測定した。
また、下記評価基準(評点)に基づき、重合深度を評価した。
結果を表1に示す。
下記評価基準において、重合深度に最も優れる評点は「A」である。
A:重合深度が40mm以上であった。
B:重合深度が40mm未満、35mm以上であった。
C:重合深度が35mm未満、30mm以上であった。
D:重合深度が30mm未満、25mm以上であった。
E:重合深度が25mm未満であった。
中でも、光増感剤として、クマリン誘導体を用いた実施例4及び実施例5、並びに、アントラセン誘導体及びナフタレン誘導体を併用した実施例6、8及び11は重合深度に優れていた。
一方、表1には示していないが、アントラセン誘導体とナフタレン誘導体を併用した実施例6、8及び11は、クマリン誘導体を用いた実施例4及び実施例5より硬化物の着色が抑制されていた。
さらに、還元剤としてアミンを用いず、ベンゾジオキソール又はその誘導体を用いた実施例1~11は、還元剤としてアミンを用いた実施例12と比較して安定性に優れていた。
また、過酸化物としてハイドロパーオキサイドを用いた実施例10は重合深度に優れていた。
一方、光ラジカル発生剤を含まない比較例1、光塩基発生剤及び過酸化物を含まない比較例2、過酸化物を含まない比較例3、光塩基発生剤を含まない比較例4及び比較例5は重合深度に劣っていた。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
Claims (17)
- 過酸化物と、光塩基発生剤と、光ラジカル発生剤と、を含む光重合開始剤。
- 前記光ラジカル発生剤が、波長420nm~525nmのいずれかの光で励起される請求項1に記載の光重合開始剤。
- 前記光ラジカル発生剤が、ノリッシュII型開始剤、又は、アニリン化合物及びヨードニウム塩化合物である請求項1又は請求項2に記載の光重合開始剤。
- 前記過酸化物が、ジアシルパーオキサイド化合物、パーオキシエステル化合物、ハイドロパーオキサイド化合物、無機過酸化物及びアルキル過酸化物からなる群より選択される少なくとも1つを含む請求項1~請求項3のいずれか1項に記載の光重合開始剤。
- 前記光塩基発生剤が、オキシムエステル化合物、アシル化合物、カルバメート化合物、アミノアセトフェノン化合物、3級アミン化合物、4級アンモニウム塩化合物及びアミド化合物からなる群より選択される少なくとも1つを含む請求項1~請求項4のいずれか1項に記載の光重合開始剤。
- ベンゾジオキソール化合物をさらに含む請求項1~請求項5のいずれか1項に記載の光重合開始剤。
- 歯科材料用の請求項1~請求項6のいずれか1項に記載の光重合開始剤。
- 請求項1~請求項7のいずれか1項に記載の光重合開始剤と、
重合性単量体と、
を含む光硬化性組成物。 - 前記重合性単量体の全量に対する前記光ラジカル発生剤の含有質量比が、0.0001~1.0である請求項8に記載の光硬化性組成物。
- 前記重合性単量体の全量に対する前記光塩基発生剤の含有質量比が、0.0001~5.0である請求項8又は請求項9に記載の光硬化性組成物。
- 前記重合性単量体の全量に対する前記過酸化物の含有質量比が、0.001~5.0である請求項8~請求項10のいずれか1項に記載の光硬化性組成物。
- フィラーをさらに含む請求項8~請求項11のいずれか1項に記載の光硬化性組成物。
- 前記フィラーが、1MHz、25℃における比誘電率が8.0以下であるフィラーを含む請求項12に記載の光硬化性組成物。
- 前記フィラーが、シリカ、バリウムボロシリケートガラス、及びアルミノシリケートガラスからなる群から選択される1つ以上のフィラーを含む請求項12又は請求項13に記載の光硬化性組成物。
- 歯科材料用の請求項8~請求項14のいずれか1項に記載の光硬化性組成物。
- 請求項8~請求項14のいずれか1項に記載の光硬化性組成物の硬化物。
- 請求項16に記載の硬化物からなる歯科材料。
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EP3895681A1 (en) | 2021-10-20 |
US20220087906A1 (en) | 2022-03-24 |
JPWO2020153269A1 (ja) | 2021-10-21 |
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