JP4494854B2 - Dental cationic curable composition - Google Patents
Dental cationic curable composition Download PDFInfo
- Publication number
- JP4494854B2 JP4494854B2 JP2004131431A JP2004131431A JP4494854B2 JP 4494854 B2 JP4494854 B2 JP 4494854B2 JP 2004131431 A JP2004131431 A JP 2004131431A JP 2004131431 A JP2004131431 A JP 2004131431A JP 4494854 B2 JP4494854 B2 JP 4494854B2
- Authority
- JP
- Japan
- Prior art keywords
- dental
- compound
- oxetane
- curable composition
- cationic
- 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 - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 55
- 125000002091 cationic group Chemical group 0.000 title claims description 26
- -1 alkenyl ether compound Chemical class 0.000 claims description 95
- 239000000178 monomer Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000003566 oxetanyl group Chemical group 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 19
- 239000003505 polymerization initiator Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000001033 ether group Chemical group 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 15
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 19
- 125000000524 functional group Chemical group 0.000 description 18
- 150000003254 radicals Chemical class 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 10
- 101100278747 Caenorhabditis elegans dve-1 gene Proteins 0.000 description 9
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- 150000001768 cations Chemical class 0.000 description 5
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- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
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- MXZKHBKVIJMSHZ-UHFFFAOYSA-N 5,12-dimethyltetracene Chemical compound C1=CC=C2C=C3C(C)=C(C=CC=C4)C4=C(C)C3=CC2=C1 MXZKHBKVIJMSHZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000000386 donor Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
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- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
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- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- JERBUBCQUQOHIC-UHFFFAOYSA-N (1-acetyloxy-9,10-dioxoanthracen-2-yl) acetate Chemical compound C1=CC=C2C(=O)C3=C(OC(C)=O)C(OC(=O)C)=CC=C3C(=O)C2=C1 JERBUBCQUQOHIC-UHFFFAOYSA-N 0.000 description 1
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- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyethers (AREA)
- Dental Preparations (AREA)
- Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
Description
本発明は歯科用材料、特に歯科用充填修復材料として好適に使用されるカチオン硬化性組成物に関する。 The present invention relates to a cationically curable composition suitably used as a dental material, particularly as a dental filling restorative material.
齲蝕や破折等により損傷をうけた歯牙の修復においては、一般にコンポジットレジンと呼ばれる光硬化性の複合充填修復材料が、その操作の簡便さや審美性の高さから汎用されている。このようなコンポジットレジンは、通常、重合性単量体、フィラー（充填材）及び重合開始剤からなり、重合性単量体としては、その光重合性の良さから（メタ）アクリレート系のラジカル重合性単量体が用いられている。 In the restoration of a tooth damaged by caries or fracture, a photocurable composite filling restoration material called a composite resin is generally used because of its easy operation and high aesthetics. Such a composite resin is usually composed of a polymerizable monomer, a filler (filler), and a polymerization initiator, and the polymerizable monomer is a (meth) acrylate radical polymerization due to its good photopolymerizability. Sex monomers are used.
歯科治療において審美性の高さは重要な要件である。一般に、歯科用コンポジットレジンの使用形態としては口腔内に充填、その後、硬化させる手法が主流であるが、その硬化前後で色調の変化が大きいと、充填時（硬化前）には周囲の歯の色調と一致していたのに、硬化させると色調が変化してしまうと良好な審美性を得ることが困難となる（変色の度合いを示すΔＥ＊が１．５以下であれば通常は肉眼では確認できないと言われている）。また、治療直後の審美性のみならず、その審美性が使用に伴って低下することのないことも求められる。口腔内で用いられる歯科用材料は、食物由来の各種着色物質などによって容易に変着色してしまうことも避ける必要がある。 In dental treatment, high aesthetics is an important requirement. In general, the main use of dental composite resins is to fill the oral cavity and then harden. However, if there is a large change in color tone before and after curing, the surrounding teeth will be filled (before curing). Although it was consistent with the color tone, it would be difficult to obtain good aesthetics if the color tone changed when cured (if the ΔE * indicating the degree of discoloration is 1.5 or less, usually with the naked eye) It is said that it cannot be confirmed). Moreover, not only the aesthetics immediately after a treatment but also that the aesthetics do not decrease with use is required. It is necessary to avoid that the dental material used in the oral cavity is easily discolored by various coloring substances derived from food.
しかしながら、ラジカル重合性単量体は、酸素による重合阻害を受けるため、口腔内で重合・硬化させた際には、表面に未重合層や重合度の低い層が残存し、この未重合層のために経時的に着色・変色し、充分な審美性を得にくいという問題がある。このため、硬化後にこの未重合層を研磨し、取り除かなければならない。 However, since radically polymerizable monomers are subject to polymerization inhibition by oxygen, when polymerized and cured in the oral cavity, an unpolymerized layer or a layer with a low degree of polymerization remains on the surface. For this reason, there is a problem that coloring and discoloration with time are difficult to obtain sufficient aesthetics. For this reason, this unpolymerized layer must be polished and removed after curing.
酸素による重合阻害がない重合性単量体としては、エポキシ化合物類、オキセタン化合物類、またはビニルエーテルや１−プロペニルエーテルなどに代表されるアルケニルエーテル化合物類等のカチオン重合性単量体がある（非特許文献１）。なかでもエポキシ化合物類、オキセタン化合物類は開環重合性であるため重合収縮率が小さく、また硬化速度も速いため研究が盛んであり、歯科用コンポジットレジンにおける重合性単量体として、このような開環重合性のカチオン重合性単量体を用いる技術は既にいくつか提案されている（例えば、特許文献１〜５参照）。 Examples of the polymerizable monomer that does not inhibit the polymerization by oxygen include a cationic polymerizable monomer such as an epoxy compound, an oxetane compound, or an alkenyl ether compound represented by vinyl ether, 1-propenyl ether, etc. Patent Document 1). In particular, epoxy compounds and oxetane compounds are ring-opening polymerizable, so the polymerization shrinkage rate is small and the curing speed is fast, and research is actively conducted. As a polymerizable monomer in a dental composite resin, Several techniques using ring-opening polymerizable cationic polymerizable monomers have already been proposed (see, for example, Patent Documents 1 to 5).
しかしながら、カチオン重合性単量体は水によって重合阻害を受けるという問題を本質的に有しているため、口腔内で用いた場合には、やはり表面未重合層を生じやすく、未だ改善の余地があった。 However, since cationically polymerizable monomers inherently have the problem of being polymerized by water, when used in the oral cavity, surface unpolymerized layers are likely to form, and there is still room for improvement. there were.
他方、歯科以外の分野においてもカチオン重合性単量体は種々検討されており、上記水分による重合阻害の問題を解決すべく、特殊な構造のオキセタン化合物を用いる技術（例えば、特許文献６）や、特定の重合開始剤を用いる技術（例えば、特許文献７）が提案されている。 On the other hand, various cationic polymerizable monomers have been studied in fields other than dentistry, and a technique using an oxetane compound having a special structure (for example, Patent Document 6), A technique using a specific polymerization initiator (for example, Patent Document 7) has been proposed.
本発明は、酸素による重合阻害を受けないカチオン重合・硬化性の歯科用組成物であって、かつ特殊な重合性単量体や特定の重合開始剤を用いなくても、口腔内のような高湿度環境下でも表面未重合層を生じ難く、よって審美性に優れた硬化体が得られる歯科用の硬化性組成物を提供することを目的とする。 The present invention is a cationic polymerization / curing dental composition that does not undergo polymerization inhibition by oxygen, and can be used in the oral cavity without using a special polymerizable monomer or a specific polymerization initiator. An object of the present invention is to provide a dental curable composition that hardly forms a surface unpolymerized layer even in a high humidity environment, and thus provides a cured product having excellent aesthetics.
本発明は上記課題を解決すべく鋭意研究した結果、オキセタン化合物に対しアルケニルエーテル化合物を少量配合することにより、各々を単独で用いた場合よりも遥かに水分の影響を受け難くなることを見出し、更に検討を進めた結果、本発明を完成した。 As a result of diligent research to solve the above-mentioned problems, the present invention has found that by blending a small amount of an alkenyl ether compound with respect to an oxetane compound, it becomes much less susceptible to moisture than when each is used alone, As a result of further investigation, the present invention was completed.
即ち、本発明は、（Ｉ）カチオン重合開始剤と（II）カチオン重合性単量体とを含む硬化性組成物において、該（II）カチオン重合性単量体は、１分子平均ａ個のオキセタン官能基を有するオキセタン化合物をＡモルと、１分子平均ｂ個のアルケニルエーテル官能基を有するアルケニルエーテル化合物をＢモルとを含んでなり、かつ、（ａ×Ａ）：（ｂ×Ｂ）が９１：９〜４０：６０の範囲にある混合物からなることを特徴とする歯科用カチオン硬化性組成物である。 That is, the present invention relates to a curable composition comprising (I) a cationic polymerization initiator and (II) a cationic polymerizable monomer, wherein (II) the cationic polymerizable monomer has an average of a molecule per molecule. A mole of oxetane compound having an oxetane functional group and B mole of an alkenyl ether compound having an average of b alkenyl ether functional groups per molecule, and (a × A) :( b × B) It is a cationic curable composition for dental use, comprising a mixture in the range of 91: 9 to 40:60.
本発明の歯科用カチオン硬化性組成物は、カチオン重合性であるため、従来歯科用として汎用されてきた（メタ）アクリレート系のラジカル重合性単量体を用いた歯科用材料と異なり酸素による重合阻害がない。さらに、オキセタン化合物とアルケニルエーテル化合物とを、各々の有する官能基が特定の割合になるように配合することにより、水分による重合阻害も起き難くなる。 Since the dental cation-curable composition of the present invention is cationically polymerizable, it is different from dental materials using (meth) acrylate radically polymerizable monomers that have been widely used for dental use in the past, and is thus polymerized with oxygen. There is no inhibition. Furthermore, by blending the oxetane compound and the alkenyl ether compound so that each of the functional groups has a specific ratio, polymerization inhibition due to moisture is less likely to occur.
また、オキセタン官能基とアルケニルエーテル官能基をさらに特定の割合にすることによって、硬化前後の色調変化も少なくなり、良好な審美性を得ることが一層容易となる。 Further, by making the oxetane functional group and the alkenyl ether functional group into a specific ratio, the change in color tone before and after curing is reduced, and it becomes easier to obtain good aesthetics.
本発明のカチオン硬化性組成物には、（Ｉ）カチオン重合開始剤と（II）カチオン重合性単量体とが含まれる。 The cationic curable composition of the present invention includes (I) a cationic polymerization initiator and (II) a cationic polymerizable monomer.
当該（Ｉ）カチオン重合開始剤は特に限定されるものではなく、公知の如何なるカチオン重合開始剤でもよい。このようなカチオン重合開始剤としては、ルイス酸或いはブレンステッド酸、又は加熱や光照射によりルイス酸或いはブレンステッド酸を生じる化合物などが知られている。口腔内などの環境で速やかに重合させることが容易な点で、光照射によりルイス酸或いはブレンステッド酸を生じる、所謂、光酸発生剤を採用することが特に好適である。 The (I) cationic polymerization initiator is not particularly limited, and any known cationic polymerization initiator may be used. As such cationic polymerization initiators, Lewis acids or Bronsted acids, or compounds that generate Lewis acids or Bronsted acids by heating or light irradiation are known. It is particularly preferable to employ a so-called photoacid generator that generates a Lewis acid or a Bronsted acid by light irradiation because it can be polymerized quickly in an environment such as the oral cavity.
当該光酸発生剤としては、ジアリールヨードニウム塩系化合物、スルホニウム塩系化合物、スルホン酸エステル化合物、およびハロメチル置換−S−トリアジン有導体等が挙げられる。 Examples of the photoacid generator include diaryl iodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and halomethyl-substituted S-triazine conductors.
これらの中でも、ジアリールヨードニウム塩系化合物及びスルホニウム塩系化合物が、重合活性が特に高い点で優れている。ジアリールヨードニウム塩系化合物の具体例を例示すれば、ジフェニルヨードニウム、ビス（ｐ−クロロフェニル）ヨードニウム、ジトリルヨードニウム、ビス（ｐ−ｔｅｒｔ−ブチルフェニル）ヨードニウム、ｐ−イソプロピルフェニル−ｐ−メチルフェニルヨードニウム、ビス（ｍ−ニトロフェニル）ヨードニウム、ｐ−ｔｅｒｔ−ブチルフェニルフェニルヨードニウム、ｐ−メトキシフェニルフェニルヨードニウム、ビス（ｐ−メトキシフェニル）ヨードニウム、ｐ−オクチルオキシフェニルフェニルヨードニウム、ｐ−フェノキシフェニルフェニルヨードニウム等のカチオンと、クロリド、ブロミド、p−トルエンスルホナート、トリフルオロメタンスルホナート、テトラフルオロボレート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレート、ヘキサフルオロフォスフェート、ヘキサフルオロアルセナート、ヘキサフルオロアンチモネート等のアニオンからなるジアリールヨードニウム塩系化合物が挙げられる。 Among these, diaryliodonium salt compounds and sulfonium salt compounds are excellent in that the polymerization activity is particularly high. Specific examples of diaryliodonium salt compounds include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium, Bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, etc. Cation and chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenyl volley And diaryl iodonium salt compounds comprising anions such as tetrakispentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate.
これらのなかでも、重合性単量体に対する溶解性の点から、p−トルエンスルホナート、トリフルオロメタンスルホナート、テトラフルオロボレート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレート、ヘキサフルオロフォスフェート、ヘキサフルオロアルセナート、ヘキサフルオロアンチモネートをアニオンとして有する化合物が好適に使用でき、また、求核性が低く、光照射を行わなければ重合性単量体との混合物として安定に保存できる点で、ヘキサフルオロアンチモネート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレートをアニオンとして有する化合物が好適に使用できる。 Among these, p-toluene sulfonate, trifluoromethane sulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenyl gallate, hexafluorophosphate, hexagonal from the viewpoint of solubility in polymerizable monomers. A compound having fluoroarsenate or hexafluoroantimonate as an anion can be suitably used, and it has low nucleophilicity, and can be stably stored as a mixture with a polymerizable monomer without light irradiation. A compound having fluoroantimonate, tetrakispentafluorophenylborate or tetrakispentafluorophenylgallate as an anion can be preferably used.
また、スルホニウム塩系化合物としては、ジメチルフェナシルスルホニウム、ジメチルベンジルスルホニウム、ジメチル−４−ヒドロキシフェニルスルホニウム、ジメチル−４−ヒドロキシナフチルスルホニウム、ジメチル−４，７−ジヒドロキシナフチルスルホニウム、ジメチル−４，８−ジヒドロキシナフチルスルホニウム、トリフェニルスルホニウム、ｐ−トリルジフェニルスルホニウム、ｐ−ｔｅｒｔ−ブチルフェニルジフェニルスルホニウム、ジフェニル−４−フェニルチオフェニルスルホニウム等のカチオンと、クロリド、ブロミド、p−トルエンスルホナート、トリフルオロメタンスルホナート、テトラフルオロボレート、テトラキスペンタフルオロフェニルボレート、テトラキスペンタフルオロフェニルガレート、ヘキサフルオロフォスフェート、ヘキサフルオロアルセナート、ヘキサフルオロアンチモネート等のアニオンとからなるスルホニウム塩系化合物が挙げられる。 Examples of sulfonium salt compounds include dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8- Cations such as dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl-4-phenylthiophenylsulfonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate , Tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexaful Examples thereof include sulfonium salt compounds composed of anions such as orophosphate, hexafluoroarsenate and hexafluoroantimonate.
これら光酸発生剤は必要に応じて、１種または２種以上混合して用いても何等差し支えない。これら光酸発生剤の使用量は、光照射により重合を開始しうる量であれば特に制限されることはないが、適度な重合の進行速度と得られる硬化体の各種物性（例えば、耐候性や硬度）を両立させるために、一般的にはカチオン重合性単量体１００質量部に対し、０．００１〜１０質量部を用いればよく、好ましくは０．０５〜５質量部を用いるとよい。 These photoacid generators may be used singly or in combination as needed. The amount of these photoacid generators used is not particularly limited as long as the polymerization can be initiated by light irradiation. However, an appropriate polymerization progress rate and various physical properties of the resulting cured product (for example, weather resistance) In general, 0.001 to 10 parts by mass, preferably 0.05 to 5 parts by mass is used with respect to 100 parts by mass of the cationic polymerizable monomer. .
上記のような光酸発生剤は通常、近紫外〜可視域には吸収の無い化合物も多く、重合反応を励起するためには、特殊な光源が必要となる場合が多い。そのため、近紫外〜可視域に吸収をもつ化合物を増感剤として、上記光酸発生剤に加えてさらに配合することが好ましい。 The photoacid generators as described above usually have many compounds that do not absorb in the near ultraviolet to visible range, and a special light source is often required to excite the polymerization reaction. Therefore, it is preferable that a compound having absorption in the near ultraviolet to visible region is further added as a sensitizer in addition to the photoacid generator.
このような増感剤として用いられる化合物は、例えばアクリジン系色素、ベンゾフラビン系色素、アントラセン、ペリレン等の縮合多環式芳香族化合物、フェノチアジン等が挙げられる。 Examples of the compound used as such a sensitizer include acridine dyes, benzoflavine dyes, condensed polycyclic aromatic compounds such as anthracene and perylene, and phenothiazine.
これら増感剤のなかでも、重合活性が良好な点で、縮合多環式芳香族化合物が好ましく、さらに、少なくとも１つの水素原子を有する飽和炭素原子が縮合多環式芳香族環と結合した構造を持つ縮合多環式芳香族化合物が好適である。 Among these sensitizers, a condensed polycyclic aromatic compound is preferable in terms of good polymerization activity, and a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to the condensed polycyclic aromatic ring. Condensed polycyclic aromatic compounds having are preferred.
このような少なくとも１つの水素原子を有する飽和炭素原子が縮合多環式芳香族環と結合した構造を持つ縮合多環式芳香族化合物を具体的に例示すると、１−メチルナフタレン、１−エチルナフタレン、１，４−ジメチルナフタレン、アセナフテン、１，２，３，４−テトラヒドロフェナントレン、１，２，３，４−テトラヒドロアントラセン、ベンゾ［ｆ］フタラン、ベンゾ［ｇ］クロマン、ベンゾ［ｇ］イソクロマン、Ｎ−メチルベンゾ［ｆ］インドリン、Ｎ−メチルベンゾ［ｆ］イソインドリン、フェナレン、４，５−ジメチルフェナントレン、１，８−ジメチルフェナントレン、アセフェナントレン、１−メチルアントラセン、９−メチルアントラセン、９−エチルアントラセン、９−シクロヘキシルアントラセン、９，１０−ジメチルアントラセン、９，１０−ジエチルアントラセン、９，１０−ジシクロヘキシルアントラセン、９−メトキシメチルアントラセン、９−(１−メトキシエチル)アントラセン、９−ヘキシルオキシメチルアントラセン、９，１０−ジメトキシメチルアントラセン、９−ジメトキシメチルアントラセン、９−フェニルメチルアントラセン、９−（１−ナフチル）メチルアントラセン、９−ヒドロキシメチルアントラセン、９−（１−ヒドロキシエチル）アントラセン、９，１０−ジヒドロキシメチルアントラン、９−アセトキシメチルアントラセン、９−（１−アセトキシエチル）アントラセン、９，１０−ジアセトキシメチルアントラセン、９−ベンゾイルオキシメチルアントラセン、９，１０−ジベンゾイルオキシメチルアントラセン、９−エチルチオメチルアントラセン、９−（１−エチルチオエチル）アントラセン、９，１０−ビス（エチルチオメチル）アントラセン、９−メルカプトメチルアントラセン、９−（１−メルカプトエチル）アントラセン、９，１０−ビス（メルカプトメチル）アントラセン、９−エチルチオメチル−１０−メチルアントラセン、９−メチル−１０−フェニルアントラセン、９−メチル−１０−ビニルアントラセン、９−アリルアントラセン、９，１０−ジアリルアントラセン、９−クロロメチルアントラセン、９−ブロモメチルアントラセン、９−ヨードメチルアントラセン、９−（１−クロロエチル）アントラセン、９−（１−ブロモエチル）アントラセン、９−（１−ヨードエチル）アントラセン、９，１０−ジクロロメチルアントラセン、９，１０−ジブロモメチルアントラセン、９，１０−ジヨードメチルアントラセン、９−クロロ−１０−メチルアントラセン、９−クロロ−１０−エチルアントラセン，９−ブロモ−１０−メチルアントラセン、９−ブロモ−１０−エチルアントラセン、９−ヨード−１０−メチルアントラセン、９−ヨード−１０−エチルアントラセン、９−メチル−１０−ジメチルアミノアントラセン、アセアンスレン、７，１２−ジメチルベンズ（ａ）アントラセン、７，１２−ジメトキシメチルベンズ（ａ）アントラセン、５，１２−ジメチルナフタセン、コラントレン、３−メチルコラントレン、７−メチルベンゾ（ａ）ピレン、３，４，９，１０−テトラメチルペリレン、３，４，９，１０−テトラキス（ヒドロキシメチル）ペリレン、ビオランスレン、イソビオランスレン、５，１２−ジメチルナフタセン、６，１３−ジメチルペンタセン、８，１３−ジメチルペンタフェン、５，１６−ジメチルヘキサセン、９，１４−ジメチルヘキサフェン等が挙げられる。 Specific examples of such condensed polycyclic aromatic compounds having a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to a condensed polycyclic aromatic ring include 1-methylnaphthalene and 1-ethylnaphthalene. 1,4-dimethylnaphthalene, acenaphthene, 1,2,3,4-tetrahydrophenanthrene, 1,2,3,4-tetrahydroanthracene, benzo [f] phthalane, benzo [g] chroman, benzo [g] isochroman, N-methylbenzo [f] indoline, N-methylbenzo [f] isoindoline, phenalene, 4,5-dimethylphenanthrene, 1,8-dimethylphenanthrene, acephenanthrene, 1-methylanthracene, 9-methylanthracene, 9-ethylanthracene , 9-cyclohexylanthracene, 9,10-dimethyl Luanthracene, 9,10-diethylanthracene, 9,10-dicyclohexylanthracene, 9-methoxymethylanthracene, 9- (1-methoxyethyl) anthracene, 9-hexyloxymethylanthracene, 9,10-dimethoxymethylanthracene, 9- Dimethoxymethylanthracene, 9-phenylmethylanthracene, 9- (1-naphthyl) methylanthracene, 9-hydroxymethylanthracene, 9- (1-hydroxyethyl) anthracene, 9,10-dihydroxymethylanthracene, 9-acetoxymethylanthracene 9- (1-acetoxyethyl) anthracene, 9,10-diacetoxymethylanthracene, 9-benzoyloxymethylanthracene, 9,10-dibenzoyloxymethylanthracene, 9 -Ethylthiomethylanthracene, 9- (1-ethylthioethyl) anthracene, 9,10-bis (ethylthiomethyl) anthracene, 9-mercaptomethylanthracene, 9- (1-mercaptoethyl) anthracene, 9,10-bis (Mercaptomethyl) anthracene, 9-ethylthiomethyl-10-methylanthracene, 9-methyl-10-phenylanthracene, 9-methyl-10-vinylanthracene, 9-allylanthracene, 9,10-diallylanthracene, 9-chloro Methyl anthracene, 9-bromomethylanthracene, 9-iodomethylanthracene, 9- (1-chloroethyl) anthracene, 9- (1-bromoethyl) anthracene, 9- (1-iodoethyl) anthracene, 9,10-dichloromethylanthracene 9,10-dibromomethylanthracene, 9,10-diiodomethylanthracene, 9-chloro-10-methylanthracene, 9-chloro-10-ethylanthracene, 9-bromo-10-methylanthracene, 9-bromo-10 -Ethylanthracene, 9-iodo-10-methylanthracene, 9-iodo-10-ethylanthracene, 9-methyl-10-dimethylaminoanthracene, acanthrene, 7,12-dimethylbenz (a) anthracene, 7,12- Dimethoxymethylbenz (a) anthracene, 5,12-dimethylnaphthacene, collanthrene, 3-methylcholanthrene, 7-methylbenzo (a) pyrene, 3,4,9,10-tetramethylperylene, 3,4,9, 10-tetrakis (hydroxymethyl) perylene, bio Nsuren, Isoviolanthrone Ren, 5,12-dimethyl-naphthacene, 6,13-dimethyl pentacene, 8,13- dimethyl penta Fen, 5,16- dimethyl hexamethylene Sen, 9,14- dimethyl hexa Fen and the like.
また上記以外の縮合多環式芳香族化合物としては、ナフタレン、フェナントレン、アントラセン、ナフタセン、ベンズ[a]アントラセン、ピレン、ペリレン等が挙げられる。 Examples of the condensed polycyclic aromatic compound other than the above include naphthalene, phenanthrene, anthracene, naphthacene, benz [a] anthracene, pyrene, perylene and the like.
これら縮合多環式芳香族化合物のなかでも、生体に対する為害性を考慮すると可視光で重合を励起することが可能となる、可視域に吸収を有する化合物が好ましく、可視域に極大吸収を有する化合物がより好ましい。また、これら縮合多環式芳香族化合物は必要に応じて複数の化合物を併用しても良い。 Among these condensed polycyclic aromatic compounds, a compound having absorption in the visible range is preferable and a compound having maximum absorption in the visible range, which can excite polymerization with visible light in consideration of harm to the living body. Is more preferable. Further, these condensed polycyclic aromatic compounds may be used in combination with a plurality of compounds as necessary.
縮合多環式芳香族化合物の添加量も、組み合わせる他の成分や重合性単量体の種類によって異なるが、通常は前期した光酸発生剤１モルに対し、縮合多環式芳香族化合物が０．００１〜２０モルであり、０．００５〜１０モルであることが好ましい。 The addition amount of the condensed polycyclic aromatic compound also varies depending on the other components to be combined and the kind of the polymerizable monomer, but the amount of the condensed polycyclic aromatic compound is usually 0 with respect to 1 mol of the above-mentioned photoacid generator. 0.001 to 20 mol, and preferably 0.005 to 10 mol.
さらに上記縮合多環式芳香族化合物に加えて、酸化型の光ラジカル発生剤を配合すると、より一層重合活性が向上し好ましい。酸化型の光ラジカル発生剤とは、光照射により励起してラジカルを発生する化合物であって、励起により水素供与体から水素を引き抜いてラジカルを生成するいわゆる水素引き抜き型のラジカル発生剤、励起により自己開裂を起こしてラジカルを発生し（自己開裂型ラジカル発生剤）、次いで該ラジカルが電子供与体から電子を引き抜くタイプのもの、及び光照射により励起して電子供与体から直接電子を引き抜いてラジカルとなるもの等の、光照射による励起によって活性ラジカル種を発生させる機構が酸化剤的な作用による（自らは還元される）ものである光ラジカル発生剤である。これら酸化型の光ラジカル発生剤は特に制限されず、公知の化合物を用いれば良いが、光照射を行った際の重合活性が他の化合物に比してより高い点で、水素引き抜き型の光ラジカル発生剤が好ましく、なかでも、ジアリールケトン化合物、α−ジケトン化合物又はケトクマリン化合物が特に好ましい。 Furthermore, it is preferable to add an oxidized photoradical generator in addition to the condensed polycyclic aromatic compound because the polymerization activity is further improved. An oxidized photoradical generator is a compound that generates radicals when excited by light irradiation, and is a so-called hydrogen abstraction type radical generator that generates radicals by extracting hydrogen from a hydrogen donor by excitation. Generates radicals by causing self-cleavage (self-cleaving radical generator), and then the radicals withdrawing electrons from the electron donor, and radicals that are excited by light irradiation and withdraw electrons directly from the electron donor. The photoradical generator is a mechanism that generates active radical species by excitation by light irradiation, such as the following. These oxidation type photo radical generators are not particularly limited, and known compounds may be used. However, in terms of higher polymerization activity when irradiated with light compared to other compounds, hydrogen abstraction type light radical generators may be used. A radical generator is preferred, and among them, a diaryl ketone compound, an α-diketone compound or a ketocoumarin compound is particularly preferred.
ジアリールケトン化合物を具体的に例示すると４，４−ビス（ジメチルアミノ）ベンゾフェノン、９−フルオレノン、３，４−ベンゾ―９−フルオレノン、２―ジメチルアミノ―９−フルオレノン、２−メトキシ―９―フルオレノン、２−クロロ―９−フルオレノン、２，７−ジクロロ―９―フルオレノン、２−ブロモ―９―フルオレノン、２，７−ジブロモ―９―フルオレノン、２−ニトロ−９−フルオレノン、２−アセトキ−９−フルオレノン、ベンズアントロン、アントラキノン、１，２−ベンズアントラキノン、２−メチルアントラキノン、２−エチルアントラキノン、１−ジメチルアミノアントラキノン、２，３−ジメチルアントラキノン、２−tert−ブチルアントラキノン、１−クロロアントラキノン、２−クロロアントラキノン、１，５−ジクロロアントラキノン、１，２−ジメトキシアントラキノン、１，２−ジアセトキシ−アントラキノン、５，１２−ナフタセンキノン、６、１３−ペンタセンキノン、キサントン、チオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、９（１０Ｈ）−アクリドン、９−メチル−９（１０Ｈ）−アクリドン、ジベンゾスベレノン等を挙げることができる。 Specific examples of the diaryl ketone compound include 4,4-bis (dimethylamino) benzophenone, 9-fluorenone, 3,4-benzo-9-fluorenone, 2-dimethylamino-9-fluorenone, and 2-methoxy-9-fluorenone. 2-chloro-9-fluorenone, 2,7-dichloro-9-fluorenone, 2-bromo-9-fluorenone, 2,7-dibromo-9-fluorenone, 2-nitro-9-fluorenone, 2-acetoxy-9 -Fluorenone, benzanthrone, anthraquinone, 1,2-benzanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 1-dimethylaminoanthraquinone, 2,3-dimethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone 1,5-dichloroanthraquinone, 1,2-dimethoxyanthraquinone, 1,2-diacetoxy-anthraquinone, 5,12-naphthacenequinone, 6,13-pentacenequinone, xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2-chlorothioxanthone, 9 (10H) -acridone, 9-methyl-9 (10H) -acridone, dibenzosuberenone and the like can be mentioned.
α−ジケトン化合物の具体例を例示すれば、カンファーキノン、ベンジル、ジアセチル、アセチルベンゾイル、２，３−ペンタジオン、２，３−オクタジオン、４，４’−ジメトキシベンジル、４，４’−オキシベンジル、９，１０−フェナンスレンキノン、アセナフテンキノン等が挙げられる。 Specific examples of α-diketone compounds include camphorquinone, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, 9,10-phenanthrenequinone, acenaphthenequinone, etc. are mentioned.
またケトクマリン化合物としては、３−ベンゾイルクマリン、３−（４−メトキシベンゾイル）クマリン、３−ベンゾイル−７−メトキシクマリン、３−（４−メトキシベンゾイル）７−メトキシ−３−クマリン、３−アセチル−７−ジメチルアミノクマリン、３−ベンゾイル−７−ジメチルアミノクマリン、３，３’−クマリノケトン、３，３’−ビス（７−ジエチルアミノクマリノ）ケトン等を挙げることができる。 Examples of ketocoumarin compounds include 3-benzoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-methoxybenzoyl) 7-methoxy-3-coumarin, and 3-acetyl- Examples thereof include 7-dimethylaminocoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3,3′-coumarinoketone, 3,3′-bis (7-diethylaminocoumarino) ketone, and the like.
これら酸化型の光ラジカル発生剤は単独または２種類以上を混合して用いて使用できる。また、添加量も組み合わせる他の成分や重合性単量体の種類によって異なるが、通常は前記した光酸発生剤１モルに対し、光ラジカル発生剤が０．００１〜２０モルであり、０．００５〜１０モルであることが好ましい。 These oxidized photoradical generators can be used alone or in admixture of two or more. Moreover, although the addition amount varies depending on the other components to be combined and the kind of the polymerizable monomer, the photoradical generator is usually 0.001 to 20 mol relative to 1 mol of the photoacid generator described above. It is preferable that it is 005-10 mol.
本発明のカチオン硬化性組成物は、（II）カチオン重合性単量体として、オキセタン官能基を有するオキセタン化合物（以下、単にオキセタン化合物）と、アルケニルエーテル官能基を有するアルケニルエーテル化合物（以下、単にアルケニルエーテル化合物）の双方を含んでいる必要がある。 The cationic curable composition of the present invention comprises (II) an oxetane compound having an oxetane functional group (hereinafter simply referred to as an oxetane compound) and an alkenyl ether compound having an alkenyl ether functional group (hereinafter simply referred to as a cation polymerizable monomer). Both alkenyl ether compounds).
なお、オキセタン官能基とは、下記式（１） The oxetane functional group is represented by the following formula (1)
（式中、ｎは０〜６の整数であり、Ｒ１は１価の基であり、ｎが２〜６の場合には、該Ｒ１は各々同一でも異なっていても良い。）
で示される四員環エーテル（オキセタン環）官能基であり、アルケニルエーテル官能基とは、下記式（２）
(In the formula, n is an integer of 0 to 6, R 1 is a monovalent group, and when n is 2 to 6, each R 1 may be the same or different.)
Is a four-membered ring ether (oxetane ring) functional group represented by the following formula (2):
（式中、Ｒ２は置換基を有していても良いアルキル基を示し、Ｒ３、Ｒ４、Ｒ５は各々独立に水素原子又は１価の基を示す。）
で示されるアルケニルエーテルからなる官能基である。
(In the formula, R 2 represents an alkyl group which may have a substituent, and R 3 , R 4 and R 5 each independently represents a hydrogen atom or a monovalent group.)
Is a functional group composed of an alkenyl ether.
本発明で使用されるオキセタン化合物は、カチオン重合可能な化合物であれば特に限定されることはなく公知の化合物を使用することができるが、上記式（１）において、１個又は２個のＲ１がオキセタン環の３位に結合しており、他方、他の位置にはＲ１が結合していない化合物が好ましい。当該オキセタン化合物を具体的に例示すると、３−メチル−３−オキセタニルメタノール、３−エチル−３−オキセタニルメタノール、３−エチル−３−フェノキシメチルオキセタン、３，３−ジエチルオキセタン、３−エチル−３−（２−エチルヘキシルオキシ）オキセタン等の１つのオキセタン環を有すもの、１，４−ビス（３−エチル−３−オキセタニルメチルオキシ）ベンゼン、４，４′−ビス（３−エチル−３−オキセタニルメチルオキシ）ビフェニール、４，４′−ビス（３−エチル−３−オキセタニルメチルオキシメチル）ビフェニール、エチレングリコールビス（３−エチル−３−オキセタニルメチル）エーテル、ビス（３−エチル−３−オキセタニルメチル）ジフェノエート、トリメチロールプロパントリス（３−エチル−３−オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３−エチル−３−オキセタニルメチル）エーテル等、あるいは下記に示す化合物 The oxetane compound used in the present invention is not particularly limited as long as it is a compound capable of cationic polymerization, and a known compound can be used. In the above formula (1), one or two R A compound in which 1 is bonded to the 3-position of the oxetane ring while R 1 is not bonded to other positions is preferred. Specific examples of the oxetane compound include 3-methyl-3-oxetanylmethanol, 3-ethyl-3-oxetanylmethanol, 3-ethyl-3-phenoxymethyloxetane, 3,3-diethyloxetane, and 3-ethyl-3. Those having one oxetane ring such as-(2-ethylhexyloxy) oxetane, 1,4-bis (3-ethyl-3-oxetanylmethyloxy) benzene, 4,4'-bis (3-ethyl-3- Oxetanylmethyloxy) biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethyloxymethyl) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanyl) Methyl) diphenoate, trimethylolpropane tris (3-ethyl) 3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, or a compound shown below
等のオキセタン環を２つ以上有す化合物が挙げられる。これらオキセタン化合物は、複数種のものを併用しても良い。 And compounds having two or more oxetane rings. These oxetane compounds may be used in combination.
特に得られる硬化体の物性の点から、１分子中にオキセタン官能基を２つ以上有するものが好適に使用される。 In particular, those having two or more oxetane functional groups in one molecule are suitably used from the viewpoint of physical properties of the obtained cured product.
また、アルケニルエーテル化合物もまた、カチオン重合可能な化合物であれば特に限定されることはなく公知のものが使用できるが、前記式（２）において、Ｒ３、Ｒ４、Ｒ５が各々独立に水素原子又はアルキル基である化合物が好ましく、入手の容易さからＲ３、Ｒ４、Ｒ５がすべて水素原子の化合物（ビニルエーテル化合物）が望ましい。 The alkenyl ether compound is not particularly limited as long as it is a compound capable of cationic polymerization, and any known alkenyl ether compound can be used. In the formula (2), R 3 , R 4 , and R 5 are each independently selected. A compound that is a hydrogen atom or an alkyl group is preferable, and a compound (vinyl ether compound) in which R 3 , R 4 , and R 5 are all hydrogen atoms is desirable from the viewpoint of availability.
代表的なアルケニルエーテル化合物を具体的に例示すれば、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、イソブチルビニルエーテル、ｔ−ブチルビニルエーテル、２−エチルヘキシルビニルエーテル、ドデシルビニルエーテル、２−クロロエチルビニルエーテル、４−ヒドロキシブチルビニルエーテル、シクロヘキシルビニルエーテル、グリシジルビニルエーテル、１，４−シクロヘキサンジメタノールモノビニルエーテル、エチレングリコールメチルビニルエーテル、トリエチレングリコールメチルビニルエーテル、エチレングリコールモノビニルエーテル、エチレングリコールフェニルビニルエーテル、エチル−１−プロペニルエーテル、ヘキシル−１−プロペニルエーテル、２−エチルヘキシル−１−プロペニルエーテル、１−メトキシ−１，３−ブタンジエン、２−（１−プロペニルオキシメチル）−１、３−ジオキソラン−２−オン等のアルケニルエーテル官能基を1つ有する化合物、また、 Specific examples of typical alkenyl ether compounds include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 2-chloroethyl vinyl ether, 4- Hydroxybutyl vinyl ether, cyclohexyl vinyl ether, glycidyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, ethylene glycol methyl vinyl ether, triethylene glycol methyl vinyl ether, ethylene glycol monovinyl ether, ethylene glycol phenyl vinyl ether, ethyl-1-propenyl ether, hexyl- 1-propenyl ether, 2- Hexyl-1-propenyl ether, 1-methoxy-1,3-butadiene, 2- (1-propenyloxy) -1,3-dioxolan-2-one or the like compound having one alkenyl ether functional group, also,
等のアルケニルエーテル官能基を二つ有する化合物、更に A compound having two alkenyl ether functional groups such as
等の、１分子中にアルケニルエーテル官能基を三つ以上有する化合物が挙げられる。これらアルケニルエーテル化合物は、異なる種類のものを複数用いても良い。 And compounds having three or more alkenyl ether functional groups in one molecule. A plurality of different types of these alkenyl ether compounds may be used.
本発明における最大の特徴は、組成物中におけるオキセタン官能基の量と、アルケニルエーテル官能基の量とが特定の範囲となるよう、オキセタン化合物とアルケニルエーテル化合物の配合量を調整する点にある。即ち、オキセタン化合物が１分子平均ａ個のオキセタン官能基を有し、アルケニルエーテル化合物が１分子平均ｂ個のアルケニルエーテル官能基を有する場合、（ａ×Ａ）：（ｂ×Ｂ）が９１：９〜４０：６０の範囲となるように、オキセタン化合物をＡモルと、アルケニルエーテル化合物をＢモル配合する必要がある。 The greatest feature of the present invention is that the blending amount of the oxetane compound and the alkenyl ether compound is adjusted so that the amount of the oxetane functional group and the amount of the alkenyl ether functional group in the composition are in a specific range. That is, when the oxetane compound has an average of a oxetane functional group of 1 molecule and the alkenyl ether compound has an average of b alkenyl ether functional groups of 1 molecule, (a × A) :( b × B) is 91: It is necessary to blend A mole of the oxetane compound and B mole of the alkenyl ether compound so as to be in the range of 9-40: 60.
なお、前述したように本発明においては、オキセタン化合物は単一のものを用いても良いし、異なる種類のものを複数用いても良い。オキセタン化合物として単一のものを用いた場合、あるいはその有するオキセタン官能基数が同一のオキセタン化合物のみを用いた場合の、上記一分子平均のオキセタン官能基数は、該オキセタン化合物の有するオキセタン官能基の数に等しい。一分子当たりの官能基の数の異なる化合物を用いた際には、上記オキセタン官能基の数は、その配合量（比）と各々の化合物が有する官能基の数とから求める平均値である。例えば、オキセタン官能基を１つだけ有すオキセタン化合物と、２つ有すオキセタン化合物を等モル量用いた場合には、１分子平均１．５個のオキセタン官能基を有するオキセタン化合物を用いたものとして計算する。同様に、オキセタン官能基を１つだけ有すオキセタン化合物と２つ有すオキセタン化合物をモル比にして１：３の割合で用いた場合には、１分子平均１．７５個のオキセタン官能基を有するオキセタン化合物を用いたものとして計算する。 As described above, in the present invention, a single oxetane compound may be used, or a plurality of different types may be used. When a single oxetane compound is used, or when only oxetane compounds having the same number of oxetane functional groups are used, the average number of oxetane functional groups per molecule is the number of oxetane functional groups of the oxetane compound. be equivalent to. When compounds having different numbers of functional groups per molecule are used, the number of oxetane functional groups is an average value obtained from the blending amount (ratio) and the number of functional groups possessed by each compound. For example, when equimolar amounts of an oxetane compound having only one oxetane functional group and an oxetane compound having two oxetane functional groups are used, an oxetane compound having an average of 1.5 oxetane functional groups per molecule is used. Calculate as Similarly, when a 1: 3 molar ratio of an oxetane compound having only one oxetane functional group and an oxetane compound having two oxetane functional groups is used, an average of 1.75 oxetane functional groups per molecule is used. Calculated as using the oxetane compound possessed.
アルケニルエーテル化合物の一分子あたりの平均官能基数も、上記と同様にして算出すればよい。 The average number of functional groups per molecule of the alkenyl ether compound may be calculated in the same manner as described above.
また、本発明において、オキセタン化合物、アルケニルエーテル化合物のいずれも、各々必ず１つ以上のオキセタン官能基、アルケニルエーテル官能基を有するから、上記ａ、ｂのいずれも１未満になることはない。化合物の入手の容易さや、本発明の硬化性組成物の粘度等の操作性、硬化後の硬化体の機械的物性等を考慮すると、ａ、ｂのいずれもが１〜５の範囲にあることが好ましく、１．５〜３の範囲にあることがより好ましい。 In the present invention, each of the oxetane compound and the alkenyl ether compound always has at least one oxetane functional group and alkenyl ether functional group, and therefore, neither a nor b is less than 1. Considering the availability of the compound, the operability such as the viscosity of the curable composition of the present invention, the mechanical properties of the cured product after curing, both a and b are in the range of 1 to 5. Is preferable, and it is more preferable that it is in the range of 1.5 to 3.
上述の通り、本発明においては（ａ×Ａ）：（ｂ×Ｂ）が９１：９〜４０：６０の範囲にあることが必須である。この範囲にすることにより、重合反応に対する水分の影響を大幅に低減することができ、口腔内のような高湿度条件下でも使用可能となる。さらに、（ａ×Ａ）：（ｂ×Ｂ）を５０：５０よりもアルケニルエーテル官能基の割合を小さくすることにより、硬化前後の色調変化が小さくなるため好ましい。他方、アルケニルエーテルは極めてカチオン重合性の高い官能基であるため、該官能基の割合が高い方がより良好な硬化性が得られる。本発明において好ましくは、（ａ×Ａ）：（ｂ×Ｂ）が８５：１５〜５０：５０の範囲であり、より好ましくは８５：１５〜５５：４５の範囲である。 As described above, in the present invention, it is essential that (a × A) :( b × B) is in the range of 91: 9 to 40:60. By making it in this range, the influence of moisture on the polymerization reaction can be greatly reduced, and it can be used even under high humidity conditions such as in the oral cavity. Furthermore, (a × A) :( b × B) is preferably reduced by reducing the ratio of the alkenyl ether functional group to 50:50, since the change in color tone before and after curing is reduced. On the other hand, since alkenyl ether is a functional group having extremely high cationic polymerizability, better curability can be obtained with a higher proportion of the functional group. In the present invention, (a × A) :( b × B) is preferably in the range of 85:15 to 50:50, more preferably in the range of 85:15 to 55:45.
本発明のカチオン硬化性組成物には、本発明の効果を損なわない範囲で、オキセタン化合物及びアルケニルエーテル化合物に加えて、他のカチオン重合性官能基を有する化合物が配合されていても良いが、硬化性組成物中のカチオン重合性官能基中に占める他のカチオン重合性官能基の割合が増えるほど、硬化速度が遅くなったりするため、カチオン硬化性組成物中の全カチオン重合性官能基の総和を１００モル％としたとき、その他の官能基の占める割合は３０モル％未満であることが好ましく、１０モル％未満であることが好ましく、５モル％未満であることが更に好ましく、オキセタン官能基及びアルケニルエーテル官能基以外の他のカチオン重合性官能基は実質的に存在しないことが特に好ましい。 In the cation curable composition of the present invention, in addition to the oxetane compound and the alkenyl ether compound, a compound having another cation polymerizable functional group may be blended as long as the effects of the present invention are not impaired. As the proportion of other cationic polymerizable functional groups in the cationic polymerizable functional group in the curable composition increases, the curing rate decreases. When the total is 100 mol%, the proportion of other functional groups is preferably less than 30 mol%, preferably less than 10 mol%, more preferably less than 5 mol%, and oxetane functionality. It is particularly preferred that there is substantially no other cationically polymerizable functional group other than the group and the alkenyl ether functional group.
また、必要に応じて（メタ）アクリレート系単量体等の付加重合型のラジカル重合性単量体を配合することも可能である。ラジカル重合性単量体を配合することにより、さらに見かけの硬化時間を短くすることができる。一方、付加重合型のラジカル重合性は酸素により重合阻害をうけるため、あまり多量に配合することは好ましくない。ラジカル重合性単量体を配合する場合のその配合量は、カチオン重合性単量体とラジカル重合性単量体の合計１００質量％に対して、３０質量％以下とすることが好ましく、１０質量％以下とすることが好ましい。 Moreover, it is also possible to mix | blend an addition polymerization type radical polymerizable monomer, such as a (meth) acrylate type monomer, as needed. By blending the radically polymerizable monomer, the apparent curing time can be further shortened. On the other hand, addition polymerization type radical polymerizability is inhibited by polymerization due to oxygen, so it is not preferable to add too much. When the radical polymerizable monomer is blended, the blending amount is preferably 30% by mass or less with respect to a total of 100% by mass of the cationic polymerizable monomer and the radical polymerizable monomer. % Or less is preferable.
このようなラジカル重合性単量体を具体的に例示すれば、メチル（メタ）アクリレート、グリシジル（メタ）アクリレート、２−シアノメチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、アリル（メタ）アクリレート、２−ヒドロキシエチルモノ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ノナエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、２，２−ビス［４−（メタ）アクリロイルオキシエトキシフェニル］プロパン、２，２−ビス［４−（メタ）アクリロイルオキシエトキシエトキシフェニル］プロパン、２，２−ビス｛４−［３−（メタ）アクリロイルオキシ−２−ヒドロキシプロポキシ］フェニル｝プロパン、１，４−ブタンジオールジ（メタ）アクリレート、１，３−ヘキサンジオールジ（メタ）アクリレート、ウレタンジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート等の（メタ）アクリレート系単量体等を挙げることができる。 Specific examples of such radical polymerizable monomers include methyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and allyl (meth) acrylate. 2-hydroxyethyl mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxye Xylphenyl] propane, 2,2-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 1,4-butanediol di (meth) acrylate, 1,3-hexanediol di ( And (meth) acrylate monomers such as (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane di (meth) acrylate.
本発明の歯科用カチオン硬化性組成物には、上記重合開始剤及び重合性単量体に加えて、歯科用硬化性組成物の配合成分として公知の他の成分を配合することができる。 In addition to the polymerization initiator and the polymerizable monomer, the dental cation curable composition of the present invention can be blended with other components known as a compounding component of the dental curable composition.
代表的な他の配合成分としては（III）充填材が挙げられる。本発明の歯科用カチオン硬化性組成物に充填材を配合することにより、重合収縮をさらに小さくすることができる。また、充填材を用いることにより、硬化前の硬化性組成物の操作性を改良したり、あるいは、硬化後の機械的物性の向上を計ることができ、特に歯科用の充填修復材料として有用性の高いものとなる。 Typical other compounding ingredients include (III) filler. By blending a filler with the dental cationic curable composition of the present invention, polymerization shrinkage can be further reduced. In addition, by using a filler, it is possible to improve the operability of the curable composition before curing, or to improve the mechanical properties after curing, especially useful as a filling restoration material for dental use. Will be expensive.
本発明の歯科用カチオン硬化性組成物に対して充填材を配合する場合、その充填材の種類や配合量は、該組成物の用途に応じて適宜設定すればよい。例えば、本発明の歯科用カチオン硬化性組成物を充填修復材料として用いる場合には、歯科用充填修復材料の充填材として公知の充填材を配合すればよい。 When a filler is blended with the dental cation-curable composition of the present invention, the type and blending amount of the filler may be appropriately set according to the use of the composition. For example, when the dental cationic curable composition of the present invention is used as a filling restorative material, a known filler may be blended as a filler for the dental filling restorative material.
より具体的には、石英、シリカ、アルミナ、シリカチタニア、シリカジルコニア、ランタンガラス、バリウムガラス、ストロンチウムガラス等の無機粒子（以下、無機フィラー）が挙げられる。さらに、これら無機フィラーと重合性単量体を予め混合し、ペースト状にした後、重合させ、粉砕して得られる粒状の有機−無機複合粒子（有機−無機複合フィラー）を用いてもよい。なお、無機フィラーとして、ジルコニア等の重金属を含むものを用いることによってＸ線造影性を付与することもできる。 More specifically, inorganic particles (hereinafter referred to as “inorganic filler”) such as quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass can be used. Furthermore, you may use the granular organic-inorganic composite particle (organic-inorganic composite filler) obtained by mixing these inorganic fillers and a polymerizable monomer in advance, forming a paste, polymerizing, and pulverizing. In addition, X-ray contrast property can also be provided by using what contains heavy metals, such as a zirconia, as an inorganic filler.
これら充填材の粒径、形状は特に限定されず、一般的に歯科用材料として使用されている、球状や不定形の、平均粒子径０．０１μｍ〜１００μｍの粒子を目的に応じて適宜使用すればよい。また、これら充填材の屈折率も特に限定されず、一般的な歯科用組成物の充填材が有する１．４〜１．７の範囲のものが制限なく使用できる。 The particle diameter and shape of these fillers are not particularly limited, and spherical or irregular particles having an average particle diameter of 0.01 μm to 100 μm, which are generally used as dental materials, can be appropriately used depending on the purpose. That's fine. Further, the refractive index of these fillers is not particularly limited, and those in the range of 1.4 to 1.7 which the fillers of general dental compositions have can be used without limitation.
本発明のカチオン硬化性組成物に上記充填材を配合する場合の配合量も特に限定されないが、歯科用充填修復材料として用いる場合には、前記重合性単量体１００質量部に対して、５０〜１５００質量部、好ましくは７０〜１０００質量部とすることが好ましい。さらに、これら無機フィラー、有機−無機複合フィラー等の充填材は各々単独で用いても良いし、材質、粒径、形状等の異なる複数種のものを併用しても良い。硬化後の機械的物性に優れる点で、歯科用充填修復材料として用いる場合には、無機フィラーを主とすることが特に好ましい。 The blending amount when the above filler is blended with the cationic curable composition of the present invention is not particularly limited, but when used as a dental filling restorative material, it is 50 per 100 parts by weight of the polymerizable monomer. To 1500 parts by mass, preferably 70 to 1000 parts by mass. Further, these fillers such as inorganic fillers and organic-inorganic composite fillers may be used alone, or a plurality of fillers having different materials, particle sizes, shapes, etc. may be used in combination. When using as a dental filling / restoring material, it is particularly preferable to mainly use an inorganic filler in terms of excellent mechanical properties after curing.
また必要に応じてポリメチルメタクリレート、ポリエチルメタクリレート、メチルメタクリレート−エチルメタクリレート共重合体、架橋型ポリメチルメタクリレート、架橋型ポリエチルメタクリレート、エチレン−酢酸ビニル共重合体、スチレン−ブタジエン共重合体、アクリロニトリル−スチレン共重合体、アクリロニトリル−ブタジエン−スチレン共重合体等の有機高分子からなる粒子（有機フィラー）を充填材として配合することも可能である。 If necessary, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile -It is also possible to mix | blend the particle | grains (organic filler) which consist of organic polymers, such as a styrene copolymer and an acrylonitrile-butadiene-styrene copolymer, as a filler.
さらに本発明の歯科用カチオン硬化性組成物には、本発明の効果を損なわない範囲で、重合禁止剤、重合禁止剤、酸化防止剤、紫外線吸収剤、染料、帯電防止剤、顔料、香料、有機溶媒や増粘剤等の公知の添加剤が配合されていても良い。 Further, the dental cationic curable composition of the present invention includes a polymerization inhibitor, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a dye, an antistatic agent, a pigment, a fragrance, and the like within a range not impairing the effects of the present invention. Known additives such as organic solvents and thickeners may be blended.
本発明の歯科用カチオン重合性組成物は上記のような歯科用充填修復材料として特に好適に使用されるが、それに限定されるものではなく、歯科用接着材や義歯床用材料等その他の用途にも使用できる。 The dental cationic polymerizable composition of the present invention is particularly preferably used as the dental filling / restoration material as described above, but is not limited thereto, and other uses such as a dental adhesive and a denture base material. Can also be used.
本発明の歯科用カチオン硬化性組成物の製造方法は特に制限されるものではなく、公知の製造方法を適宜採用すればよい。具体的には、本発明の歯科用カチオン硬化性組成物を構成する、カチオン重合開始剤、カチオン重合性単量体ならびに必要に応じて配合されるその他の配合成分を所定量秤取り、これらを混合すればよい。 The manufacturing method of the dental cation-curable composition of the present invention is not particularly limited, and a known manufacturing method may be adopted as appropriate. Specifically, a predetermined amount of a cationic polymerization initiator, a cationic polymerizable monomer, and other blending components blended as necessary, which constitute the dental cation-curable composition of the present invention, are weighed out. What is necessary is just to mix.
本発明の歯科用カチオン硬化性組成物の包装形態は特に制限されるものではなく、その目的や保存安定性を考慮して適宜決定すればよい。例えば、カチオン重合開始剤として光カチオン重合開始剤を配合した際には、本発明の歯科用カチオン硬化性組成物を構成する全ての成分を遮光状態で一つの包装とすればよい。一方、光照射を行わずとも室温でカチオン重合を開始できるような成分を重合開始剤として用いる場合には、保存中に重合・硬化してしまわないように、２つ以上の包装に分割しておき、使用直前に両者を混合するような形態が好ましい。 The packaging form of the dental cationic curable composition of the present invention is not particularly limited, and may be appropriately determined in consideration of its purpose and storage stability. For example, when a photocationic polymerization initiator is blended as a cationic polymerization initiator, all the components constituting the dental cation-curable composition of the present invention may be made into one package in a light-shielded state. On the other hand, if a component that can start cationic polymerization at room temperature without light irradiation is used as a polymerization initiator, it can be divided into two or more packages to prevent polymerization and curing during storage. A form in which both are mixed immediately before use is preferred.
本発明の歯科用カチオン硬化性組成物を硬化させる手段としては用いたカチオン重合開始剤の重合開始機構に従い適宜、公知の重合手段を採用すればよく、具体的には、カーボンアーク、キセノンランプ、メタルハライドランプ、タングステンランプ、蛍光灯、太陽光、ヘリウムカドミウムレーザー、アルゴンレーザー等の光源による光照射、或いは加熱重合器等を用いた加熱、またはこれらを組み合わせた方法等が何等制限なく使用される。光照射により重合させる場合には、その照射時間は、光源の波長、強度、硬化体の形状や材質によって異なるため、予備的な実験によって予め決定しておけばよいが、一般には、照射時間が５〜６０秒程度の範囲になるように、各種成分の配合割合を調整しておくことが好ましい。同様に加熱時間及び加熱温度も予備的な実験によって予め決定しておけばよい。 As a means for curing the dental cationic curable composition of the present invention, a known polymerization means may be appropriately employed according to the polymerization initiation mechanism of the used cationic polymerization initiator. Specifically, a carbon arc, a xenon lamp, A metal halide lamp, a tungsten lamp, a fluorescent lamp, light irradiation with a light source such as sunlight, helium cadmium laser, and argon laser, heating using a heating polymerizer, or a combination of these is used without any limitation. In the case of polymerization by light irradiation, the irradiation time varies depending on the wavelength of the light source, the intensity, the shape and material of the cured body, and therefore may be determined in advance by preliminary experiments. It is preferable to adjust the blending ratio of the various components so that the range is about 5 to 60 seconds. Similarly, the heating time and heating temperature may be determined in advance by preliminary experiments.
以下、実施例により本発明を具体的に示すが、本発明はこの実施例によって何等限定されるものではない。尚、本文中、並びに実施例中に使用した化合物の略称は以下の通りである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. The abbreviations of the compounds used in the text and in the examples are as follows.
１．オキセタン化合物 1. Oxetane compounds
２．アルケニルエーテル化合物 2. Alkenyl ether compounds
３．ラジカル重合性単量体 3. Radical polymerizable monomer
５．光酸発生剤 5. Photoacid generator
６．縮合多環芳香族化合物 6). Fused polycyclic aromatic compounds
７．酸化型の光ラジカル発生剤
ＣＱ：カンファーキノン。
7). Oxidized photoradical generator CQ: camphorquinone.
８．その他
ＤＭＰＴ：ｐ−ジメチルアミノトルイジン。
ＤＭＢＥ：４−ジメチルアミノエチル安息香酸エチル。
8). Other DMPT: p-dimethylaminotoluidine.
DMBE: ethyl 4-dimethylaminoethyl benzoate.
また実施例、比較例における各種物性の評価方法を以下に示す。なお、硬化に際しての雰囲気条件は、温度２２℃、相対湿度２０％を条件１、温度３７℃、相対湿度１００％を条件２とした。条件２は口腔内の環境を想定した雰囲気である。 Moreover, the evaluation method of the various physical properties in an Example and a comparative example is shown below. In addition, the atmosphere conditions at the time of curing were as follows: a temperature of 22 ° C. and a relative humidity of 20% as a condition 1; a temperature of 37 ° C. and a relative humidity of 100% as a condition 2. Condition 2 is an atmosphere that assumes the environment in the oral cavity.
（１）表面未重合
条件１又は条件２の雰囲気下で、６ｍｍφ×０．３ｍｍの孔を有するポリテトラフルオロエチレン製のモールドの底面に、パスツールピペットを用いて硬化性組成物を塗布した。同様に組成物液面上面約５ｍｍの距離から歯科用可視光線照射器（トクヤマデンタル社、パワーライト）にて６０秒間光照射し、光硬化させた。硬化体の照射面にべたつきがある物を×、べたつきは無いが表面が白化しているものを△、べたつきおよび白化がないものを○とした。
(1) Surface Unpolymerization In the atmosphere of Condition 1 or Condition 2, the curable composition was applied to the bottom of a polytetrafluoroethylene mold having 6 mmφ × 0.3 mm holes using a Pasteur pipette. Similarly, light irradiation was performed for 60 seconds with a dental visible light irradiator (Tokuyama Dental Co., Powerlight) from a distance of about 5 mm on the upper surface of the composition liquid, and the composition was photocured. An object with stickiness on the irradiated surface of the cured product was marked with ×, a thing with no stickiness but with a whitened surface was marked with △, and a thing with no stickiness and whitening was marked with ◯.
（２）微小硬度
条件１又は条件２の雰囲気下で、６ｍｍφ×１．５ｍｍの孔を有するポリテトラフルオロエチレン製のモールドに硬化性組成物が平らになるように充填した。雰囲気中に３分間放置し、その後、ポリプロピレンフィルムで覆い、さらにスライドグラスで圧接した状態で、充填面上５ｍｍの位置から歯科用可視光線照射器にて６０秒間光照射し、光硬化させた。硬化後、ポリプロピレンフィルムを剥がし、微小硬度計ＭＨＴ−１（松沢精機株式会社製）、加重２００ｇ、加重時間３０秒にて照射面の硬度を測定した。
(2) Microhardness Under the atmosphere of Condition 1 or Condition 2, a mold made of polytetrafluoroethylene having 6 mmφ × 1.5 mm holes was filled so that the curable composition was flat. It was left in the atmosphere for 3 minutes, then covered with a polypropylene film, and further pressed with a slide glass, and then light-cured by irradiation with a dental visible light irradiator from a position of 5 mm on the filling surface for 60 seconds. After curing, the polypropylene film was peeled off, and the hardness of the irradiated surface was measured with a micro hardness meter MHT-1 (manufactured by Matsuzawa Seiki Co., Ltd.), a weight of 200 g, and a weight time of 30 seconds.
（３）硬化体の変色
６ｍｍφ×１．５ｍｍの孔を有するポリテトラフルオロエチレン製のモールドに硬化性組成物を充填し、ポリプロピレンフィルムで覆い、この未硬化の状態で分光色差計（カラーアナライザーＴＣ−１８００ＭＫ−ＩＩ）を用い、黒バックにてＬ＊ ０、ａ＊ ０、ｂ＊ ０を測定した。
(3) Discoloration of cured body A polytetrafluoroethylene mold having a 6 mmφ × 1.5 mm hole is filled with a curable composition, covered with a polypropylene film, and in this uncured state, a spectrocolorimeter (color analyzer TC). −1800MK-II), L * 0 , a * 0 , and b * 0 were measured with a black background.
別途、条件１の雰囲気下で６ｍｍφ×１．５ｍｍの孔を有するポリテトラフルオロエチレン製のモールドに硬化性組成物を充填し、ポリプロピレンフィルムで覆い、さらにスライドグラスで圧接した状態で、充填面上５ｍｍの位置から歯科用可視光線照射器にて６０秒間光照射し、光硬化させた。硬化後、モールドから取り出し、分光色差計にてＬ＊、ａ＊、ｂ＊を測定し、下記式に従って硬化前後の色差（ΔＥ＊）を算出した。
ΔＥ＊＝｛（Ｌ＊−Ｌ＊ ０）２＋（ａ＊−ａ＊ ０）２＋（ｂ＊−ｂ＊ ０）２｝１／２
また、この試料片表面を硬化前の組成物と比較し、著しく着色している物を×、極僅かに着色している物を○、肉眼では着色が確認できない物を◎とした。
Separately, fill the curable composition in a mold made of polytetrafluoroethylene having 6 mmφ × 1.5 mm holes under the condition 1 condition, cover with a polypropylene film, and press-contact with a slide glass. Light was cured by irradiating light from a position of 5 mm with a dental visible light irradiator for 60 seconds. After curing, the product was removed from the mold, L * , a * , b * were measured with a spectral color difference meter, and the color difference (ΔE * ) before and after curing was calculated according to the following formula.
ΔE * = {(L * −L * 0 ) 2 + (a * −a * 0 ) 2 + (b * −b * 0 ) 2 } 1/2
In addition, the surface of the sample piece was compared with the composition before curing, the markedly colored product was marked with x, the slightly colored product was marked with ◯, and the color that could not be confirmed with the naked eye was marked with ◎.
（４）曲げ強度・曲げ弾性率
条件１の雰囲気下で硬化性組成物を２×２×２５ｍｍの金型に充填し、ポリプロピレンフィルムで覆い、光照射器にて１．５分間光照射し硬化させた。硬化物を３７℃で一晩保存した後、オートグラフ（島津製作所社製）を使用し、支点間距離２０ｍｍ、クロスヘッドスピード０．５ｍｍ／分で３点曲げ強度と曲げ弾性率を各々５個の硬化物について測定し、その平均値を算出した。
(4) Flexural strength and flexural modulus Fill the 2 × 2 × 25 mm mold with the curable composition in the atmosphere of condition 1, cover with a polypropylene film, and cure by light irradiation for 1.5 minutes with a light irradiator. I let you. After storing the cured product at 37 ° C. overnight, using an autograph (manufactured by Shimadzu Corporation), the distance between the fulcrums is 20 mm and the crosshead speed is 0.5 mm / min. The cured product was measured and the average value was calculated.
実施例１
相対湿度２０％以下の環境下でＯＸ−１とＤＶＥ−１とを、ＯＸ−１が１モルに対して、ＤＶＥ−１が０．１１１モルとなるように量を調節して配合した。この場合、ＯＸ−１は２官能のオキセタン化合物であるからａが２であり、ＤＶＥ−１は二官能のアルケニルエーテル化合物であるからｂが２であるから、（ａ×Ａ）：（ｂ×Ｂ）＝（２×１）：（２×０．１１１）＝９０：１０である。
Example 1
In an environment with a relative humidity of 20% or less, OX-1 and DVE-1 were blended by adjusting the amounts such that DVE-1 was 0.111 mol with respect to 1 mol of OX-1. In this case, since OX-1 is a bifunctional oxetane compound, a is 2, and since DVE-1 is a bifunctional alkenyl ether compound, b is 2, (a × A): (b × B) = (2 × 1) :( 2 × 0.111) = 90: 10.
暗所下、この重合性単量体の混合物１００質量部に対し、重合開始剤としてＩＭＤＰＩを０．１質量部、ＤＭＢＡｎを０．０３質量部、カンファーキノンを０．０３質量部加え均一になるまで攪拌・溶解した。表面未重合及び変色について評価した結果を表１に示す。 In a dark place, 100 parts by mass of the polymerizable monomer mixture is uniformly added with 0.1 parts by mass of IMDPI, 0.03 parts by mass of DMBAn and 0.03 parts by mass of camphorquinone as a polymerization initiator. Stir until dissolved. Table 1 shows the results of evaluation on surface unpolymerization and discoloration.
実施例２〜４、比較例１〜７
ＯＸ−１とＤＶＥ−１との配合割合を、表１に示す官能基の割合となるよう変えた以外は実施例１と同様にして物性を評価した。結果をあわせて表１に示す。なお、表中、オキセタン化合物の欄の数値は（ａ×Ａ）＋（ｂ×Ｂ）を１００とした場合の（ａ×Ａ）を、アルケニルエーテル化合物の欄の数値は同じく（ｂ×Ｂ）を示す（以下、全ての表において同じ）。
Examples 2-4, Comparative Examples 1-7
The physical properties were evaluated in the same manner as in Example 1 except that the blending ratio of OX-1 and DVE-1 was changed to the ratio of the functional groups shown in Table 1. The results are shown in Table 1. In the table, the numerical value in the column of the oxetane compound is (a × A) when (a × A) + (b × B) is 100, and the numerical value in the column of the alkenyl ether compound is the same (b × B). (Hereinafter the same in all tables).
実施例５
重合開始剤を、ＩＭＤＰＩが０．１質量部、ＣＱが０．０３質量部、４−ジメチルアミノ安息香酸エチル０．０３質量部とした以外は実施例１と同様にして硬化性組成物を調製し物性を評価した。結果を表２に示す。
Example 5
A curable composition was prepared in the same manner as in Example 1 except that the polymerization initiator was 0.1 parts by mass of IMDPI, 0.03 parts by mass of CQ, and 0.03 parts by mass of ethyl 4-dimethylaminobenzoate. The physical properties were evaluated. The results are shown in Table 2.
実施例６〜８、比較例８〜１３
ＯＸ−１とＤＶＥ−１との配合割合を、表１に示す官能基の割合となるよう変えた以外は実施例５と同様にして物性を評価した。結果をあわせて表２に示す。
Examples 6-8, Comparative Examples 8-13
The physical properties were evaluated in the same manner as in Example 5 except that the blending ratio of OX-1 and DVE-1 was changed to the ratio of functional groups shown in Table 1. The results are shown in Table 2.
表１、２に結果を示したように、オキセタン官能基とアルケニルエーテル官能基の割合を本発明で規定する範囲にした組成物は、高湿度条件下（条件２）でも表面未重合がなく、口腔内で用いる歯科用組成物として好適な物性を有していることがわかる。さらに、アルケニルエーテル官能基の割合の少ない実施例１、２では硬化前後の色調変化も目視で確認できないほど小さく、高い審美性を要求される歯科用コンポジットレジンとして特に有用である。 As shown in Tables 1 and 2, the composition in which the ratio of the oxetane functional group to the alkenyl ether functional group is within the range specified in the present invention is free of surface unpolymerization even under high humidity conditions (Condition 2). It turns out that it has a physical property suitable as a dental composition used in an oral cavity. Furthermore, in Examples 1 and 2 with a small proportion of alkenyl ether functional groups, the change in color tone before and after curing is so small that it cannot be visually confirmed, and is particularly useful as a dental composite resin that requires high aesthetics.
他方、オキセタン官能基とアルケニルエーテル官能基の割合が、本発明で規定する範囲をはずれた場合には、オキセタン官能基、アルケニルエーテル官能基のいずれが多くても表面未重合層を生じていた。また表１に示した結果と、表２に示した結果との比較から理解されるように、重合開始剤を変更しても本発明の効果には影響がなく、本発明の効果は官能基の割合を特定の範囲とすることによって達成される。 On the other hand, when the ratio of the oxetane functional group and the alkenyl ether functional group deviated from the range specified in the present invention, a surface unpolymerized layer was formed even if either the oxetane functional group or the alkenyl ether functional group was large. Moreover, as understood from the comparison between the results shown in Table 1 and the results shown in Table 2, even if the polymerization initiator is changed, the effect of the present invention is not affected. This is achieved by making the ratio of the specific range.
実施例９
球状シリカ−ジルコニア（粒径０．５μｍ）と球状シリカ−チタニア（粒径０．１μｍ）の重量比７：３の混合物２０ｇを、ｐＨ４．０に調整した塩酸８０ｍｌに縣濁させ、攪拌しながら３−グリシジルオキシプロピルトリメトキシシラン１．２ｇを滴下した。１時間攪拌後、エバポレーターで水を留去し、得られた固体を乳鉢で粉砕後、減圧下８０℃で１５時間乾燥した。乾燥後、得られた粉末を無機フィラーａとし、シリカゲルを乾燥剤としたデシケーター中で保存した。
Example 9
20 g of a 7: 3 weight ratio mixture of spherical silica-zirconia (particle size 0.5 μm) and spherical silica-titania (particle size 0.1 μm) was suspended in 80 ml of hydrochloric acid adjusted to pH 4.0 and stirred. 1.2 g of 3-glycidyloxypropyltrimethoxysilane was added dropwise. After stirring for 1 hour, water was distilled off with an evaporator, and the obtained solid was pulverized with a mortar and then dried at 80 ° C. under reduced pressure for 15 hours. After drying, the obtained powder was used as an inorganic filler a and stored in a desiccator using silica gel as a desiccant.
一方、実施例１と同様にして、ＯＸ−１とＤＶＥ−１とを、（ａ×Ａ）：（ｂ×Ｂ）＝９０：１０となるように混合し、この混合物１００質量部に対して、重合開始剤としてＩＭＤＰＩを０．１質量部、ＤＭＢＡｎを０．０３質量部、カンファーキノンを０．０３質量部加え均一になるまで攪拌・溶解した。 On the other hand, in the same manner as in Example 1, OX-1 and DVE-1 were mixed so that (a × A) :( b × B) = 90: 10, and 100 parts by mass of this mixture was mixed. Then, 0.1 parts by mass of IMDPI, 0.03 parts by mass of DMBAn and 0.03 parts by mass of camphorquinone were added as polymerization initiators and stirred and dissolved until uniform.
この重合性単量体混合物を、室温２２℃、湿度２０％に保たれた恒温・恒湿室中で上記無機フィラーａと、無機フィラー含有率７６質量％となるようにメノウ乳鉢で混合し、該混合物を真空下、脱泡して気泡を取り除き歯科用充填修復材料を得た。この材料について、硬化後の微小硬度と硬化前後の変色について評価した。結果を表３に示す。 This polymerizable monomer mixture was mixed in an agate mortar with an inorganic filler content of 76% by mass with the inorganic filler a in a constant temperature / humidity chamber maintained at a room temperature of 22 ° C. and a humidity of 20%. The mixture was degassed under vacuum to remove bubbles and obtain a dental filling and restorative material. This material was evaluated for microhardness after curing and discoloration before and after curing. The results are shown in Table 3.
実施例１０〜１３、比較例１４〜１９
ＯＸ−１とＤＶＥ−１との配合割合を、表１に示す官能基の割合となるよう変えた以外は実施例９と同様にして歯科用充填修復材料を調製し物性を評価した。結果をあわせて表３に示す。なお、微小硬度の欄において「測定不可」とあるのは表面が極めて脆い硬化体であり、前記微小硬度計の測定下限未満の硬度であったことを表す（以下、表４、５においても同じ）。
Examples 10-13, Comparative Examples 14-19
A dental filling restorative material was prepared and its physical properties were evaluated in the same manner as in Example 9 except that the blending ratio of OX-1 and DVE-1 was changed to the ratio of functional groups shown in Table 1. The results are shown in Table 3. In the column of microhardness, “not measurable” indicates that the surface is an extremely brittle cured body and has a hardness that is less than the measurement lower limit of the microhardness meter (hereinafter the same in Tables 4 and 5). ).
実施例１４〜１７、比較例２０〜２４
オキセタン化合物としてＯＸ−１に代えてＯＸ−２を用い、表４に示す官能基割合となるようにＤＶＥ−１と混合して用いた以外は、実施例９と同様にして歯科用充填修復材料を調製し物性を評価した。結果をあわせて表４に示す。
Examples 14-17, Comparative Examples 20-24
Dental filling restorative material as in Example 9, except that OX-2 was used instead of OX-1 as the oxetane compound and was mixed with DVE-1 so as to have the functional group ratio shown in Table 4. Were prepared and the physical properties were evaluated. The results are shown in Table 4.
実施例１８〜２０、比較例２５〜２９
アルケニルエーテル化合物としてＤＶＥ−１に代えてＤＶＥ−２を用い、表５に示す官能基割合となるようにＯＸ−１と混合して用いた以外は、実施例９と同様にして歯科用充填修復材料を調製し物性を評価した。結果をあわせて表５に示す。
Examples 18-20, Comparative Examples 25-29
The dental filling restoration was carried out in the same manner as in Example 9 except that DVE-2 was used instead of DVE-1 as the alkenyl ether compound and the mixture was used with OX-1 so as to have the functional group ratio shown in Table 5. Materials were prepared and evaluated for physical properties. The results are shown in Table 5.
また、実施例１４、比較例１４及び比較例１９で調製した歯科用充填修復材料の曲げ強度及び曲げ弾性率を測定した結果を表６に示す。 Table 6 shows the results of measuring the bending strength and the flexural modulus of the dental filling and restorative materials prepared in Example 14, Comparative Example 14 and Comparative Example 19.
Claims (3)
The dental cation-curable composition according to claim 1 or 2, which is a dental filling restorative material.
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| CNA2005100922749A CN1732883A (en) | 2004-04-27 | 2005-04-27 | Cationically curable composition for dental use |
| EP05252619A EP1591098B1 (en) | 2004-04-27 | 2005-04-27 | Cationically curable composition for dental use |
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| JP2004520319A (en) * | 2000-12-22 | 2004-07-08 | ロディア・シミ | Dental compositions based on functionalized silicones crosslinkable and / or polymerizable by a heating process |
| JP2004196949A (en) * | 2002-12-18 | 2004-07-15 | Tokuyama Corp | Photopolymerization initiator composition and photopolymerization composition |
| JP2004196775A (en) * | 2002-11-12 | 2004-07-15 | Tokuyama Corp | Photocationic polymerization initiator composition and photocationic polymerizable composition |
| JP2005187385A (en) * | 2003-12-25 | 2005-07-14 | Tokuyama Corp | Cation-curable composition for dental use |
| JP2005298596A (en) * | 2004-04-08 | 2005-10-27 | Tokuyama Corp | Curable composition |
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| JP2004520319A (en) * | 2000-12-22 | 2004-07-08 | ロディア・シミ | Dental compositions based on functionalized silicones crosslinkable and / or polymerizable by a heating process |
| JP2004149587A (en) * | 2002-10-29 | 2004-05-27 | Tokuyama Corp | Photocationic polymerization initiator composition |
| JP2004196775A (en) * | 2002-11-12 | 2004-07-15 | Tokuyama Corp | Photocationic polymerization initiator composition and photocationic polymerizable composition |
| JP2004196949A (en) * | 2002-12-18 | 2004-07-15 | Tokuyama Corp | Photopolymerization initiator composition and photopolymerization composition |
| JP2005187385A (en) * | 2003-12-25 | 2005-07-14 | Tokuyama Corp | Cation-curable composition for dental use |
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