JPH0378844B2 - - Google Patents
Info
- Publication number
- JPH0378844B2 JPH0378844B2 JP59275895A JP27589584A JPH0378844B2 JP H0378844 B2 JPH0378844 B2 JP H0378844B2 JP 59275895 A JP59275895 A JP 59275895A JP 27589584 A JP27589584 A JP 27589584A JP H0378844 B2 JPH0378844 B2 JP H0378844B2
- Authority
- JP
- Japan
- Prior art keywords
- benzophenone
- tetra
- group
- tertiary
- dental
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 30
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 3
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 3
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 claims description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 claims description 2
- PCFGAJYAWWWGLT-UHFFFAOYSA-N 5-[3-carboxy-4-(2-methylpentan-2-ylperoxycarbonyl)benzoyl]-2-(2-methylpentan-2-ylperoxycarbonyl)benzoic acid Chemical compound C1=C(C(O)=O)C(C(=O)OOC(C)(C)CCC)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CCC)C(C(O)=O)=C1 PCFGAJYAWWWGLT-UHFFFAOYSA-N 0.000 claims description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 2
- YPBNDGVRPOECEP-UHFFFAOYSA-N [2-hydroxy-3-[2-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propoxy]ethoxy]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COCCOCC(O)COC(=O)C(C)=C YPBNDGVRPOECEP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- YGWAFVKXCAQAGJ-UHFFFAOYSA-N bis(2-methylpentan-2-yl) 4-[3,4-bis(2-methylpentan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CCC)C(C(=O)OOC(C)(C)CCC)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CCC)C(C(=O)OOC(C)(C)CCC)=C1 YGWAFVKXCAQAGJ-UHFFFAOYSA-N 0.000 claims description 2
- VRZQMDDQCTXMKG-UHFFFAOYSA-N bis(2-phenylpropan-2-yl) 4-[3,4-bis(2-phenylpropan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C=1C=CC=CC=1C(C)(C)OOC(=O)C1=CC=C(C(=O)C=2C=C(C(C(=O)OOC(C)(C)C=3C=CC=CC=3)=CC=2)C(=O)OOC(C)(C)C=2C=CC=CC=2)C=C1C(=O)OOC(C)(C)C1=CC=CC=C1 VRZQMDDQCTXMKG-UHFFFAOYSA-N 0.000 claims description 2
- LZZMTLWFWQRJIS-UHFFFAOYSA-N bis[2-(4-propan-2-ylphenyl)propan-2-yl] 4-[3,4-bis[2-(4-propan-2-ylphenyl)propan-2-ylperoxycarbonyl]benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=CC(C(C)C)=CC=C1C(C)(C)OOC(=O)C1=CC=C(C(=O)C=2C=C(C(C(=O)OOC(C)(C)C=3C=CC(=CC=3)C(C)C)=CC=2)C(=O)OOC(C)(C)C=2C=CC(=CC=2)C(C)C)C=C1C(=O)OOC(C)(C)C1=CC=C(C(C)C)C=C1 LZZMTLWFWQRJIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Chemical group 0.000 claims description 2
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims 3
- 239000000463 material Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- -1 benzoin alkyl ether Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003479 dental cement Substances 0.000 description 2
- 239000002978 dental impression material Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NENAMKMSJOINIR-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl) 4-[3,4-bis(2,4,4-trimethylpentan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CC(C)(C)C)C(C(=O)OOC(C)(C)CC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CC(C)(C)C)C(C(=O)OOC(C)(C)CC(C)(C)C)=C1 NENAMKMSJOINIR-UHFFFAOYSA-N 0.000 description 1
- ITXCLKMRLHBUEP-UHFFFAOYSA-N bis(2-methylbutan-2-yl) 4-[3,4-bis(2-methylbutan-2-ylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)CC)C(C(=O)OOC(C)(C)CC)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)CC)C(C(=O)OOC(C)(C)CC)=C1 ITXCLKMRLHBUEP-UHFFFAOYSA-N 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
〔産業上の利用分野〕
本発明は可視光線の照射により重合硬化が可能
な歯科用組成物に関する。本発明において歯科用
組成物とは、エチレン性不飽和化合物を含んでな
る歯冠材料、義歯床材料、歯科接着性修復材料、
歯科用印象材料などを包含する。
〔従来の技術〕
従来、これらの歯科用組成物の重合硬化方法と
しては、ベンゾイルペルオキシドと第３アミンな
どによるレドツクス系の重合開始剤を使用して硬
化させる方式と、ベンゾインアルキルエーテルな
どの光増感剤に紫外線を照射して硬化させる方式
が用いられてきた。
〔発明が解決しようとする問題点〕
レドツクス系重合開始剤を用いた常温硬化型で
は、粉一液タイプあるいはペーストーペーストタ
イプの練和方式であるために、硬化したレジン中
に気泡が入りやすく、また硬化が早くて操作時間
が短いといつた欠点があつた。他方、紫外線線硬
化型の場合は、紫外線の物質透過性が弱く、コン
ポジツトレジンの硬化深さが２mm以内に限られる
こと、320nｍ以下の短い波長の紫外線は人体へ
の為害性があるため、フイルターなどで防御する
必要があること、また、照射装置の水銀ランプが
劣化して寿命が短いことなどの問題点がある。
〔問題を解決するための手段〕
本発明者らは、前記のような欠点のない歯科用
組成物を得るために研究を重ねた結果、光重合開
始剤としてα−ジケント類とベンゾフエノン基含
有多価ペルオキシエステル類を組合せて用いるこ
とにより、可視光で重合硬化する優れた歯科用組
成物を見いだした。
すなわち、本発明は、エチレン性不飽和化合物
と、α−ジケトン類および下記一般式（）で示
されるベンゾフエノン基含有多価ペルオキシエス
テル類からなる光重合開始剤とを含んでわる可視
光線硬化性歯科用組成物を提供するものである。
（但し、R1、R′1はそれぞれ炭素数４から８の第
３アルチル基または炭素数９から12の第３アラル
キル基、R2、R′2はそれぞれ水素原子、炭素数４
から８の第３アルコキシ基または炭素数９から12
の第３アラルキルオキシ基を表わす。）
本発明に使用されるエチレン性不飽和化合物と
しては従来から歯科用組成物に用いられているエ
チレン性不飽和化合物が全て使用できるが、その
例としては、たとえばメチルメタクリレート、２
−ヒドロキシエチルメタクリレート、ネオペンチ
ルグリコールジメタクリレート、エチレングリコ
ールジメタクリレート、ジエチレングリコールジ
メタクリレート、トリエチレングリコールジメタ
クリレート、１，２−ビス（３−メタクリロキシ
−２−ヒドロキシプロポキシ）エタン、２，２−
ビス〔４−（３−メタクリロキシ−２−ヒドロキ
シプロポキシ）フエニル〕プロパン、ビスフエノ
ールＡジメタクリレート、２−ヒドロキシ−１，
３−ジメタクリロキシプロパン、ヘキサメチレン
グリコールジメタクリレート、ジ−２−メタクリ
ロキシエチル−２，２，４−トリメチルヘキサン
メチレンジカルバメートなどがある。この他にカ
ルボン酸基、リン酸基を含有したメタクリル酸エ
ステル類やアクリル酸エステル類、またスチレン
誘導体なども本発明に利用できる。
本発明に使用されるα−ジケトン類としては、
波長400nｍから700nｍに吸収極大を有するα−
ジケトン類が全て使用できるが、その例として
は、ビアセチル、２，３−ペンタジオン、２，３
−オクタジオン、ベンジル、４，4′−ジメトキシ
ベンジル、４，4′−オキシベンジル、４，4′−ジ
クロルベンジル、アセナフテンキノン、９，10−
フエナントレンキノン、カンフアーキノン、β−
ナフトキノンなどがあり、これらは１種または２
種以上混合して使用してもよく、特にアセナフテ
ンキノン、９，10−フエナントレンキノン、カン
フアーキノン、β−ナフトキノンが好ましい。
本発明に使用される一般式（）で示されるベ
ンゾフエノン基含有多価ペルオキシエステル類の
例としては、たとえば、３，3′，４，4′−テトラ
−（ｔ−ブチルペルオキシカルボニル）ベンゾフ
エノン、３，3′，４，4′−テトラ−（ｔ−アミル
ペルオキシカルボニル）ベンゾフエノン、３，
3′，４，4′−テトラ−（ｔ−ヘキシルペルオキシ
カルボニル）ベンゾフエノン、３，3′，４，4′−
テトラ−（ｔ−オクチルペルオキシカルボニル）
ベンゾフエノン、３，3′，４，4′−テトラ（クミ
ルペルオキシカルボニル）ベンゾフエノン、３，
3′，４，4′−テトラ（ｐ−イソプロピルクミルペ
ルオキシカルボニル）ベンゾフエノン、３，3′−
ジカルボキシ−４，4′−ジ（ｔ−ブチルペルオキ
シカルボニル）ベンゾフエノン、３，3′−ジカル
ボキシ−４，4′−ジ（ｔ−ヘキシルペルオキシカ
ルボニル）ベンゾフエノンなどがある。
本発明の歯科用組成物は、前記のエチレン性不
飽和化合物の１種または２種以上と、α−ジケト
ン類の１種または２種以上と、前記ベンゾフエノ
ン基含有多価ペルオキシエステル類の１種または
２種以上とを有効成分として含有するものであ
り、その組成はα−ジケトン類の濃度がエチレン
性不飽和化合物に対して0.01〜10重量％であり、
更に好ましくは0.1〜５重量％である。α−ジケ
トン類の濃度が0.01重量％未満ではα−ジケトン
類の添加効果が認められず、10重量％を越えると
α−ジケトン類が組成物中に溶解しなかつたり、
硬化深さが減少したり、また衛生上も好ましくな
い。
ベンゾフエノン基含有多価ペルオキシエステル
類の濃度はエチレン性不飽和化合物に対して0.01
〜10重量％であり、さらに好ましくは0.1〜５重
量％である。ベンゾフエノン基含有多価ペルオキ
シエステル類の濃度が0.01重量％未満ではベンゾ
フエノン基含有多価ペルオキシエステル類の添加
効果が認められず、10重量％を越えるとベンゾフ
エノン基含有多価ペルオキシエステル類が組成物
中に溶解しなかつたり、硬化物の物性が低下した
り、また衛生上も好ましくない。
本発明の歯科用組成物は、必要に応じて充填材
を適宜加えて用いてもよい。充填材としては、例
えば燐灰石、ソーダガラス、石英、シリカゲル、
硼珪酸ガラス、合成サフアイア（アルミナ）及び
放射性不透明充填材料、例えば酸化バリウム及び
ジルコニウムガラスなどがあり、球状、微粉末
状、微小板、繊維、ホイスカーであつてもよいし
又は不規則な形状を有していてもよい。さらに必
要ならば上述の成分の他に、重合禁止剤、酸化防
止剤、安定剤、顔料、増粘剤等を必要に応じ適量
添加してもよい。
本発明の歯科用組成物は、光重合開始剤として
前記α−ジケトン類とベンゾフエノン基含有多価
ペルオキシエステル類を最適に組合せて用いるこ
とにより、波長400nｍ〜700nｍの範囲の可視光
の照射により容易に硬化する。
本発明に用いる可視光線照射機は前述範囲の波
長を有する光を放射するものであれば、全て使用
可能であり、この様な光源としてはキセノン灯、
ハロゲン灯、螢光灯、タングステン灯、メタルハ
ライド灯、可視レーザー灯がある。
本発明の歯科用組成物は予め供給者により１液
に混合され、遮光された容器に充填して医師、歯
科技工士に供給される。医師または歯科技工士は
本発明の歯科用組成物を塗布、充填または成型し
た御、照射機より方放射される可視光線により重
合硬化させることができる。
〔発明の効果〕
本発明の歯科用組成物は、特定の光重合開始剤
を用いているので、可視光により短時間で容易に
硬化し、しかも硬化深さも４mm以上と歯科用とし
て優れた硬化性を有しており、さらに安全性、臨
床操作性、経済性の点でも優れている。
〔実施例〕
以下実施例および比較例により本発明をさらに
詳しく説明する。これらの実施例は説明の目的で
述べるものであつて本発明になんら制限を加える
ものではない。
実施例 １〜12
表１に示した組成比で、エチレン性不飽和化合
物にα−ジケトン類とベンゾフエノ基含有ペルオ
キシエステル類を均一に溶解して組成物とした。
この組成物を内径10mm、深さ10mmのポリエチレン
製円筒に充填し、歯科用ハロゲン灯（15V、
150W）により円筒上部３mmの距離から可視光線
を照射して重合硬化した。また放射波長の効果を
明確にするために、組成物を充填した円筒上部に
色がラスフイルターを置き、前記ハロゲン灯によ
り可視光線を照射して重合硬化した。尚、色ガラ
スフイルター（東芝(株)製）のＹ−43、Ｙ−47はそ
れぞれ透過限界波長が430nｍ、470nｍであるこ
とを示す。色ガラスフイルターを設置した場合
は、放射強度が1/2〜1/3以下に低下した。この組
成物の硬化深さは、重合硬化物を円筒から取りだ
し未反応物を除去した後、マイクロメーターを用
いて測定した。結果を表−１に示した。
表−１の結果から明らかなように、本発明の歯
科用組成物は可視光線の20〜40秒程度の短時間の
照射により、充分な硬化深さ（５mm以上）が得ら
れ、また色ガラスフイルターを設置したときの結
果から放射強度が1/2〜1/3以下に低下するにもか
かわらず470nｍ以上の非常に安全な光によつて
も効果的に重合硬化することが明らかである。こ
れらのことから、本発明の歯科用組成物が歯冠材
料、義歯床材料、歯科接着性修復材料、歯科用印
象材料として優れており、臨床操作性、安全性も
良いことがわかる。
比較例 １〜７
表−２に示した組成比で実施例と同様な試験を
行つた。結果を表−２に示したが、本発明に用い
るα−ジケトン類またはベンゾフエノン基含有多
価ペルオキシエステル類単独では充分に硬化せ
ず、また一般の有機過酸化物とα−ジケトン類を
併用しても充分に硬化せず、更に従来の紫外線用
光重合開始剤を用いても硬化しない。
[Industrial Field of Application] The present invention relates to a dental composition that can be polymerized and cured by irradiation with visible light. In the present invention, the dental composition refers to a dental crown material, a denture base material, a dental adhesive restorative material containing an ethylenically unsaturated compound,
Includes dental impression materials, etc. [Prior Art] Conventionally, methods for polymerizing and curing these dental compositions include curing using redox polymerization initiators such as benzoyl peroxide and tertiary amines, and photointensifying polymerization initiators such as benzoin alkyl ether. A method of curing the sensitizer by irradiating it with ultraviolet light has been used. [Problems to be solved by the invention] Room-temperature curing types using redox-based polymerization initiators use a one-component powder type or paste-paste type kneading system, so air bubbles tend to form in the cured resin. Another disadvantage was that it cured quickly and required a short operating time. On the other hand, in the case of ultraviolet curing type, the penetration of ultraviolet rays into materials is weak, the curing depth of the composite resin is limited to less than 2 mm, and ultraviolet rays with short wavelengths of 320 nm or less are harmful to the human body. There are problems such as the need for protection with filters, etc., and the mercury lamp used in the irradiation device deteriorates and has a short lifespan. [Means for Solving the Problems] As a result of repeated research in order to obtain a dental composition free from the above-mentioned drawbacks, the present inventors have discovered that α-dikents and benzophenone group-containing polymers have been used as photopolymerization initiators. By using a combination of polyvalent peroxyesters, we have found an excellent dental composition that is polymerized and cured by visible light. That is, the present invention provides a visible light-curable dental treatment comprising an ethylenically unsaturated compound, a photopolymerization initiator consisting of an α-diketone, and a benzophenone group-containing polyhydric peroxyester represented by the following general formula (). The present invention provides a composition for use. (However, R 1 and R' 1 are each a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, R 2 and R' 2 are each a hydrogen atom, and each is a tertiary aralkyl group having 4 to 8 carbon atoms.
to 8 tertiary alkoxy group or carbon number 9 to 12
represents a tertiary aralkyloxy group. ) As the ethylenically unsaturated compound used in the present invention, all ethylenically unsaturated compounds conventionally used in dental compositions can be used; examples thereof include methyl methacrylate, 2
-Hydroxyethyl methacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,2-bis(3-methacryloxy-2-hydroxypropoxy)ethane, 2,2-
Bis[4-(3-methacryloxy-2-hydroxypropoxy)phenyl]propane, bisphenol A dimethacrylate, 2-hydroxy-1,
Examples include 3-dimethacryloxypropane, hexamethylene glycol dimethacrylate, and di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate. In addition, methacrylic acid esters and acrylic acid esters containing a carboxylic acid group or a phosphoric acid group, styrene derivatives, etc. can also be used in the present invention. The α-diketones used in the present invention include:
α- has an absorption maximum between wavelengths 400nm and 700nm
All diketones can be used, examples include biacetyl, 2,3-pentadione, 2,3
-octadione, benzyl, 4,4'-dimethoxybenzyl, 4,4'-oxybenzyl, 4,4'-dichlorobenzyl, acenaphthenequinone, 9,10-
phenanthrenequinone, camphorquinone, β-
There are naphthoquinones, etc., and these are one or two types.
A mixture of two or more species may be used, and acenaphthenequinone, 9,10-phenanthrenequinone, camphorquinone, and β-naphthoquinone are particularly preferred. Examples of the benzophenone group-containing polyhydric peroxyesters represented by the general formula () used in the present invention include 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3 ,3',4,4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3,
3',4,4'-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-
Tetra-(t-octylperoxycarbonyl)
Benzophenone, 3,3',4,4'-tetra(cumylperoxycarbonyl)benzophenone, 3,
3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, 3,3'-
Examples include dicarboxy-4,4'-di(t-butylperoxycarbonyl)benzophenone and 3,3'-dicarboxy-4,4'-di(t-hexylperoxycarbonyl)benzophenone. The dental composition of the present invention comprises one or more of the ethylenically unsaturated compounds described above, one or more α-diketones, and one of the benzophenone group-containing polyhydric peroxyesters. or two or more types as active ingredients, and its composition is such that the concentration of α-diketones is 0.01 to 10% by weight based on the ethylenically unsaturated compound,
More preferably, it is 0.1 to 5% by weight. If the concentration of α-diketones is less than 0.01% by weight, no effect of the addition of α-diketones is observed, and if it exceeds 10% by weight, α-diketones may not be dissolved in the composition.
The curing depth decreases, and it is also unfavorable from a sanitary standpoint. The concentration of polyhydric peroxyesters containing benzophenone groups is 0.01 relative to ethylenically unsaturated compounds.
-10% by weight, more preferably 0.1-5% by weight. If the concentration of the benzophenone group-containing polyvalent peroxyester is less than 0.01% by weight, no effect of the addition of the benzophenone group-containing polyvalent peroxyester will be observed, and if it exceeds 10% by weight, the benzophenone group-containing polyvalent peroxyester will be present in the composition. It may not dissolve in water, the physical properties of the cured product may deteriorate, and it is also unfavorable from a sanitary standpoint. The dental composition of the present invention may be used by appropriately adding a filler as necessary. Examples of fillers include apatite, soda glass, quartz, silica gel,
These include borosilicate glass, synthetic sapphire (alumina) and radiopaque filling materials such as barium oxide and zirconium glasses, which may be spherical, finely powdered, platelets, fibers, whiskers, or have irregular shapes. You may do so. Furthermore, if necessary, appropriate amounts of polymerization inhibitors, antioxidants, stabilizers, pigments, thickeners, etc. may be added in addition to the above-mentioned components. The dental composition of the present invention can be easily produced by irradiation with visible light in the wavelength range of 400 nm to 700 nm by using an optimal combination of the above α-diketones and benzophenone group-containing polyhydric peroxy esters as photopolymerization initiators. hardens to. Any visible light irradiator used in the present invention can be used as long as it emits light having a wavelength within the above-mentioned range, and examples of such light sources include xenon lamps,
There are halogen lights, fluorescent lights, tungsten lights, metal halide lights, and visible laser lights. The dental composition of the present invention is mixed in advance into a single liquid by a supplier, filled into a light-shielded container, and supplied to doctors and dental technicians. A doctor or dental technician can apply, fill or mold the dental composition of the present invention and then polymerize and harden it using visible light emitted from an irradiator. [Effects of the Invention] Since the dental composition of the present invention uses a specific photopolymerization initiator, it is easily cured in a short time by visible light, and has a cure depth of 4 mm or more, which is excellent for dental use. It also has excellent safety, clinical operability, and economical efficiency. [Examples] The present invention will be explained in more detail below using Examples and Comparative Examples. These examples are provided for illustrative purposes and are not intended to limit the invention in any way. Examples 1 to 12 Compositions were prepared by uniformly dissolving α-diketones and benzopheno group-containing peroxyesters in an ethylenically unsaturated compound at the composition ratios shown in Table 1.
This composition was filled into a polyethylene cylinder with an inner diameter of 10 mm and a depth of 10 mm, and a dental halogen lamp (15 V,
Polymerization and curing were performed by irradiating visible light from a distance of 3 mm from the top of the cylinder (150W). In order to clarify the effect of radiation wavelength, a colored glass filter was placed on top of the cylinder filled with the composition, and visible light was irradiated with the halogen lamp to polymerize and cure the composition. Note that Y-43 and Y-47 of colored glass filters (manufactured by Toshiba Corporation) have transmission limit wavelengths of 430 nm and 470 nm, respectively. When a colored glass filter was installed, the radiation intensity decreased to 1/2 to 1/3 or less. The curing depth of this composition was measured using a micrometer after taking out the polymerized and cured product from the cylinder and removing unreacted materials. The results are shown in Table-1. As is clear from the results in Table 1, the dental composition of the present invention can be cured to a sufficient depth (5 mm or more) by irradiation with visible light for a short period of about 20 to 40 seconds, and can be used to cure colored glass. It is clear from the results obtained when a filter is installed that polymerization and curing can be effectively effected even with very safe light of 470 nm or more, although the radiation intensity is reduced to 1/2 to 1/3 or less. These results show that the dental composition of the present invention is excellent as a dental crown material, denture base material, dental adhesive restorative material, and dental impression material, and has good clinical operability and safety. Comparative Examples 1 to 7 Tests similar to those in Examples were conducted using the composition ratios shown in Table-2. The results are shown in Table 2, but the α-diketones or benzophenone group-containing polyhydric peroxyesters used in the present invention alone did not cure sufficiently, and the combination of general organic peroxides and α-diketones did not cure sufficiently. It does not cure sufficiently even when using a conventional ultraviolet photopolymerization initiator.
【表】【table】
【表】【table】
【表】
他の略称は表ー１と同じである
。
[Table] Other abbreviations are the same as in Table-1.
Claims (1)
および下記一般式（）で示されるベンゾフエノ
ン基含有多価ペルオキシエステル類からなる光重
合開始剤とを含んでなる可視光線硬化性歯科用組
成物。 （但し、R1、R′1はそれぞれ炭素数４から８の第
３アルキル基または炭素数９から12の第３アラル
キル基、R2、R′2はそれぞれ水素原子、炭素数４
から８の第３アルコキシ基または炭素数９から12
の第３アラルキルオキシ基を表わす。） ２ ベンゾフエノン基含有多価ペルオキシエステ
ル類が３，3′，４，4′−テトラ−（ｔ−ブチルペ
ルオキシカルボニル）ベンゾフエノン、３，3′，
４，4′−テトラ−（ｔ−アルミペルオキシカルボ
ニル）ベンゾフエノン、３，3′，４，4′−テトラ
−（ｔ−ヘキシルペルオキシカルボニル）ベンゾ
フエノン、３，3′，４，4′−テトラ−（ｔ−オク
チルペルオキシカルボニル）ベンゾフエノン、
３，3′，４，4′−テトラ−（クミルペルオキシカ
ルボニル）ベンゾフエノン、３，3′，４，4′−テ
トラ−（ｐ−イソプロピルクミルペルオキシカル
ボニル）ベンゾフエノン、３，3′−ジカルボキシ
−４，4′−ジ（ｔ−ブチルペルオキシカルボニ
ル）ベンゾフエノンおよび３，3′−ジカルボキシ
−４，4′−ジ（ｔ−ヘキシルペルオキシカルボニ
ル）ベンゾフエノンから選ばれる１または２種以
上である特許請求の範囲第１項記載の組成物。 ３ α−ジケトン類がアセナフテンキノン、９，
10−フエナントレンキノン、カンフアーキノンお
よびβ−ナフトキノンから選ばれる１種または２
種以上である特許請求の範囲第１項または第２項
記載の組成物。 ４ エチレン性不飽和化合物が、トリエチレング
リコールジメタクリレート、ヘキサメチレングリ
コールジメタクリレート、２，２−ビス〔４−
（３−メタクリロキシ−２−ヒドロキシプロポキ
シ）フエニル〕プロパン、ジ−２−メタクリロキ
シエチル−２，２，４−トリメチルヘキサメチレ
ンジカルバメートおよび１，２−ビス（３−メタ
クリロキシ−２−ヒドロキシプロポキシ）エタン
から選ばれる１種または２種以上である特許請求
の範囲第１項、第２項または第３項記載の組成
物。[Scope of Claims] 1. A visible light curable compound comprising an ethylenically unsaturated compound and a photopolymerization initiator comprising an α-diketone and a benzophenone group-containing polyhydric peroxyester represented by the following general formula (). Dental composition. (However, R 1 and R' 1 are each a tertiary alkyl group having 4 to 8 carbon atoms or a tertiary aralkyl group having 9 to 12 carbon atoms, R 2 and R' 2 are each a hydrogen atom, and each is a tertiary aralkyl group having 4 to 8 carbon atoms.
to 8 tertiary alkoxy group or carbon number 9 to 12
represents a tertiary aralkyloxy group. ) 2 benzophenone group-containing polyvalent peroxyesters are 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3',
4,4'-tetra-(t-aluminumperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-( t-octylperoxycarbonyl)benzophenone,
3,3',4,4'-tetra-(cumylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(p-isopropylcumylperoxycarbonyl)benzophenone, 3,3'-dicarboxy A patent claim that is one or more selected from -4,4'-di(t-butylperoxycarbonyl)benzophenone and 3,3'-dicarboxy-4,4'-di(t-hexylperoxycarbonyl)benzophenone The composition according to item 1. 3 α-diketones are acenaphthenequinone, 9,
One or two selected from 10-phenanthrenequinone, camphorquinone, and β-naphthoquinone
The composition according to claim 1 or 2, which is more than one species. 4 The ethylenically unsaturated compound is triethylene glycol dimethacrylate, hexamethylene glycol dimethacrylate, 2,2-bis[4-
(3-methacryloxy-2-hydroxypropoxy)phenyl]propane, di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and 1,2-bis(3-methacryloxy-2-hydroxypropoxy)ethane The composition according to claim 1, 2, or 3, which is one or more selected from the following.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59275895A JPS61158908A (en) | 1984-12-29 | 1984-12-29 | Dental composition curable with visible light |
| US06/768,546 US4746685A (en) | 1984-08-31 | 1985-08-23 | Light curable dental composition |
| EP85110961A EP0176777B1 (en) | 1984-08-31 | 1985-08-30 | Light curable dental composition |
| DE8585110961T DE3574387D1 (en) | 1984-08-31 | 1985-08-30 | Light curable dental composition |
| US07/029,287 US4824876A (en) | 1984-08-31 | 1987-03-23 | Light curable dental liquid or paste |
| US07/160,621 US4923905A (en) | 1984-08-31 | 1988-02-26 | Light curable dental composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59275895A JPS61158908A (en) | 1984-12-29 | 1984-12-29 | Dental composition curable with visible light |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61158908A JPS61158908A (en) | 1986-07-18 |
| JPH0378844B2 true JPH0378844B2 (en) | 1991-12-17 |
Family
ID=17561931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59275895A Granted JPS61158908A (en) | 1984-08-31 | 1984-12-29 | Dental composition curable with visible light |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61158908A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0757765B2 (en) * | 1985-04-23 | 1995-06-21 | 日本油脂株式会社 | Photopolymerization initiator |
-
1984
- 1984-12-29 JP JP59275895A patent/JPS61158908A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61158908A (en) | 1986-07-18 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |