JPH06689B2 - Photopolymerizable dental material - Google Patents
Photopolymerizable dental materialInfo
- Publication number
- JPH06689B2 JPH06689B2 JP61207785A JP20778586A JPH06689B2 JP H06689 B2 JPH06689 B2 JP H06689B2 JP 61207785 A JP61207785 A JP 61207785A JP 20778586 A JP20778586 A JP 20778586A JP H06689 B2 JPH06689 B2 JP H06689B2
- Authority
- JP
- Japan
- Prior art keywords
- reducing agent
- dental material
- photopolymerizable
- photosensitizer
- photopolymerizable 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
Landscapes
- Dental Preparations (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、光重合性および機械的強度の優れた光重合性
歯科材料に関する。TECHNICAL FIELD The present invention relates to a photopolymerizable dental material having excellent photopolymerizability and mechanical strength.
［従来の技術およびその問題点］ 光重合は、ラッカーおよび被覆塗装用樹脂の硬化、印刷
原版の製造および書類印刷への応用など多くの工業用途
に適用されている。[Prior Art and its Problems] Photopolymerization is applied to many industrial applications such as curing of lacquer and coating resin, production of a printing original plate, and application to document printing.
歯科領域においても、光重合性物質は歯牙充填剤、歯牙
封止材あるいは歯冠部および樹脂製義歯床の製造などに
応用されている。Also in the dental field, photopolymerizable substances are applied to the production of tooth fillers, tooth sealants or crowns and resin denture bases.
ラジカル重合性単量体と光重合触媒とから成る光重合性
材料は、特公昭５４−１０９８６号公報に記載されてい
る。それによれば、光増感剤は下記の構造を有し、 （Ａは同じであっても異なっていてもよく、炭化水素基
または置換炭化水素基であり、両方の基Ａが直接結合も
しくは二価の炭化水素基を介して一緒に結合していても
あるいは両方の基Ａが一緒になって縮合芳香族環系を形
成していてもよい）、例えば、ビアセチル、Ｐ，Ｐ′−
ジアルコキシベンジル、カンファーキノンなどが例示さ
れている。A photopolymerizable material comprising a radically polymerizable monomer and a photopolymerization catalyst is described in JP-B-54-10986. According to it, the photosensitizer has the following structure, (A may be the same or different and is a hydrocarbon group or a substituted hydrocarbon group, and both groups A may be directly bonded or bonded together via a divalent hydrocarbon group, or Both groups A may be taken together to form a fused aromatic ring system), for example biacetyl, P, P'-
Examples are dialkoxybenzyl, camphorquinone and the like.
還元剤は下記の構造を有し、上記光増感剤が励起状態に
あるときに光増感剤を還元するものである。The reducing agent has the following structure and reduces the photosensitizer when the photosensitizer is in an excited state.
（Ｒは同じであっても異なっていてもよく、水素，炭化
水素基、置換炭化水素基または２個のＲがＮと共に環系
を形成している基であり、３個のＲが同時に水素原子で
はなく、３個のＲが同時に置換炭化水素基ではなく、そ
してＮは芳香族基に対して直接に結合していない）、 具体例としては、プロピルアミン、ジメチルアミノエチ
ルメタクリレート、Ｎ，Ｎ′−ジメチルアニリン、ピペ
リジンなどが挙げられている。しかし、還元剤としてこ
れらのアミンを使用した光重合性材料は、毒性の問題で
歯科材料としては不適である。 (Rs may be the same or different and each is hydrogen, a hydrocarbon group, a substituted hydrocarbon group or a group in which two Rs form a ring system together with N, and three Rs are simultaneously hydrogen. Not an atom, three Rs are not simultaneously substituted hydrocarbon groups, and N is not directly attached to an aromatic group), specific examples are propylamine, dimethylaminoethyl methacrylate, N, N ′ -Dimethylaniline, piperidine and the like are mentioned. However, a photopolymerizable material using these amines as a reducing agent is unsuitable as a dental material due to toxicity.
［問題点を解決する手段］ 本発明は、短時間の光照射によって光重合が充分進行
し、硬度、硬化深度、曲げ強度、圧縮強度などの機械適
強度に優れ、且つ、毒性のない光重合性歯科材料に関す
る。[Means for Solving Problems] The present invention is a photopolymerization in which photopolymerization is sufficiently advanced by light irradiation for a short time, mechanical strength such as hardness, curing depth, bending strength, and compressive strength is excellent, and which is not toxic. Sex dental material.
即ち、本発明は、ラジカル重合性単量体と、光増感剤お
よび還元剤からなる光重合触媒とから成る光重合性歯科
材料であって、光増感剤がカンファーキノンであり、還
元剤が一般式［Ｉ］、 （式中R1，R2は水素原子またはアルキル基） で表されるＮ−フェニルグリシンおよびそのアルキルエ
ステルから選ばれた還元剤であることを特徴とする光重
合性歯科材料に関する。That is, the present invention is a photopolymerizable dental material comprising a radically polymerizable monomer and a photopolymerization catalyst comprising a photosensitizer and a reducing agent, wherein the photosensitizer is camphorquinone and the reducing agent. Is the general formula [I], (Wherein R 1 and R 2 are hydrogen atoms or alkyl groups) is a reducing agent selected from N-phenylglycine and alkyl esters thereof, and relates to a photopolymerizable dental material.
ラジカル重合性単量体としては、アクリル酸エステル、
メタクリル酸エステル、一価または多価アルコールなど
のエチレン性不飽和化合物の他、ウレタン−アクリレー
ト共重合体、ウレタン−メタクリレート共重合体あるい
はビスフェノールＡとグリシジルメタクリレートとの反
応生成物などが挙げられる。ラジカル重合性単量体は１
種類あるいは２種類以上を混合して使用できる。As the radically polymerizable monomer, acrylic acid ester,
In addition to ethylenically unsaturated compounds such as methacrylic acid esters and monohydric or polyhydric alcohols, urethane-acrylate copolymers, urethane-methacrylate copolymers or reaction products of bisphenol A and glycidyl methacrylate can be mentioned. Radical polymerizable monomer is 1
It is possible to use one kind or a mixture of two or more kinds.
光増感剤としては、カンファーキノンが使用される。カ
ンファーキノンはラジカル重合性単量体に対して0.００
１〜１０重量％、好ましくは0.０５〜５重量％の割合で
使用される。Camphorquinone is used as the photosensitizer. Camphorquinone is 0.00 with respect to radical polymerizable monomer
It is used in a proportion of 1 to 10% by weight, preferably 0.05 to 5% by weight.
カンファーキノンが0.００１重量％未満では、十分な光
増感効果が得られず、１０重量％を越える場合は、それ
以上光増感効果が向上せず、無意味であるばかりでな
く、得られた光重合性歯科材料の貯蔵安定性が低く好ま
しくない。When the amount of camphorquinone is less than 0.001% by weight, a sufficient photosensitizing effect cannot be obtained, and when the amount is more than 10% by weight, the photosensitizing effect is not further improved, which is not only meaningless. The obtained photopolymerizable dental material has low storage stability and is not preferable.
還元剤としては、次式［Ｉ］、 （式中Ｒ，Ｒは水素原子またはアルキル基） で表されるＮ−フェニルグリシンおよびそのアルキルエ
ステルから選ばれた少なくとも１種の還元剤が使用され
る。具体適には、Ｎ−フェニルグリシン、Ｎ−フェニル
グリシンメチル、Ｎ−フェニルグリシンエチルなどが挙
げられる。これらはほとんどすべて動物性蛋白質に含有
されるアミノ酸の１種であり、還元剤として有用である
と共に、人体に全く無害である。As the reducing agent, the following formula [I], (In the formula, R and R are hydrogen atoms or alkyl groups) At least one reducing agent selected from N-phenylglycine and its alkyl ester is used. Specific examples include N-phenylglycine, N-phenylglycine methyl, N-phenylglycine ethyl and the like. Almost all of these are one kind of amino acids contained in animal proteins, are useful as reducing agents, and are completely harmless to the human body.
還元剤はラジカル重合性単量体に対して0.００１〜１０
重量％、好ましくは0.０５〜５重量％の割合で使用され
る。The reducing agent is 0.001 to 10 with respect to the radical polymerizable monomer.
It is used in proportions by weight, preferably 0.05-5% by weight.
還元剤が0.００１重量％未満では、十分な還元効果が得
られず、１０重量％を越える場合は、得られた光重合性
歯科材料の貯蔵安定性が低く好ましくない。If the reducing agent is less than 0.001% by weight, a sufficient reducing effect cannot be obtained, and if it exceeds 10% by weight, the storage stability of the obtained photopolymerizable dental material is low, which is not preferable.
本発明の光重合性歯科材料には、慣用されている添加
剤、例えば、貯蔵安定性を維持するための安定剤、Ｘ線
造影剤、顔料などを添加できる。The photopolymerizable dental material of the present invention may be added with conventional additives such as stabilizers for maintaining storage stability, X-ray contrast agents and pigments.
本発明の光重合性歯科材料は、従来の光重合性材料と同
様に、ハロゲンランプ、キセノンランプ、螢光灯あるい
は太陽光などを光源とする光によって光重合することが
できる。The photopolymerizable dental material of the present invention can be photopolymerized by light using a halogen lamp, a xenon lamp, a fluorescent lamp, or sunlight as a light source, like the conventional photopolymerizable material.
以下に実施例により本発明を詳しく説明する。The present invention will be described in detail below with reference to examples.
実施例 暗室中で２，２−ビス［４−（３−メタクリロキシ−２
−ヒドロキシプロポキシ）−フェニル］プロパン７０重
量部とトリエチレングリコールジメタクリレート３０重
量部とを混合し、この混合液にカンファーキノンを0.２
重量％添加して光増感剤を調整した。この調整液をビー
カーに分取し、各々のビーカーに第１表に示した割合で
Ｎ−フェニルグリシンを添加し、光増感剤−還元剤系の
光重合性材料を調整した。Example 2,2-bis [4- (3-methacryloxy-2) in a dark room
-Hydroxypropoxy) -phenyl] propane (70 parts by weight) and triethylene glycol dimethacrylate (30 parts by weight) were mixed, and camphorquinone (0.2 parts) was added to the mixed solution.
The photosensitizer was adjusted by adding it in a weight percentage. This adjusted solution was dispensed into beakers, and N-phenylglycine was added to each beaker in the proportion shown in Table 1 to prepare a photosensitizer-reducing agent photopolymerizable material.
上記の如く調整した各々の光重合性材料１８部に、γ−
メタクリロキシプロピルトリメトキシシランで表面処理
をした石英粉［（株）龍森製：ＣＲＳ２１０７−０５］
８２部を添加し、メノウ乳鉢中で練和してペースト状と
した。To 18 parts of each photopolymerizable material prepared as described above, γ-
Quartz powder surface-treated with methacryloxypropyltrimethoxysilane [CRS2107-05 made by Tatsumori Co., Ltd.]
82 parts was added and kneaded in an agate mortar to form a paste.
上記ペーストを用いて各物性を以下の如くにして測定し
た。Each physical property was measured as follows using the above paste.
［硬化深度］ 厚さ１０mmのポリテトラフルオロエチレン製シートに、
直径４mmの貫通孔を設け、この孔に前記ペーストを充填
した。その表面をセロファンで覆い、歯科充填樹脂重合
用の可視光線照射装置（Ｋｕｌｚｅｒ社製、トランスラ
ックス）により３０秒間光を照射した。次いで、孔から
光照射面から重合の進んだペースト（円柱形）を取り出
し、カッターナイフで未重合部分を除去した後の長さを
測定し、硬化深度とする。[Curing depth] 10mm thick polytetrafluoroethylene sheet,
A through hole having a diameter of 4 mm was provided, and this hole was filled with the paste. The surface was covered with cellophane, and light was irradiated for 30 seconds by a visible light irradiation device for polymerizing a dental filling resin (Translux, manufactured by Kulzer). Next, the paste (cylindrical shape) in which polymerization has progressed is taken out from the hole from the light irradiation surface, and the length after removing the unpolymerized portion with a cutter knife is measured to obtain the curing depth.
［ブリネル硬度、圧縮強度］ 厚さ５mmのポリテトラフルオロエチレン製シートに、直
径４mmの貫通孔を設け、シートの片面にガラス板を当
て、反対面からこの孔に前記ペーストを充填した。その
表面をセロファンで覆い、上記照射装置により３０秒間
光を照射した。次いで、シートを裏返し、ガラス面側か
らも３０秒間光を照射した。孔から重合生成物（円柱
形）を取り出し、ブリネル硬度と圧縮強度を測定した。
測定はそれぞれＪＩＳ Ｔ６５０６およびＡＤＡ規格N
o.２７に準拠して行った。[Brinell Hardness, Compressive Strength] A sheet of polytetrafluoroethylene having a thickness of 5 mm was provided with a through hole having a diameter of 4 mm, a glass plate was applied to one side of the sheet, and the paste was filled into the hole from the opposite side. The surface was covered with cellophane, and light was irradiated by the irradiation device for 30 seconds. Next, the sheet was turned upside down, and light was irradiated from the glass surface side for 30 seconds. The polymerized product (cylindrical) was taken out from the hole, and the Brinell hardness and compressive strength were measured.
The measurements are JIS T6506 and ADA standard N, respectively.
It carried out according to o.27.
［曲げ強度］ 厚さ２mmのポリテトラフルオロエチレン製シートに、巾
２mm、長さ２５mmの方形の孔を設け、シートの片面にガ
ラス板を当て、反対面からこの孔に前記ペーストを充填
した。その表面をセロファンで覆い、歯冠用硬質樹脂重
合用の可視光線照射装置（Ｋｕｌｚｅｒ社製、デンタカ
ラーＸＳ）により９０秒間光を照射した。次いで、孔か
ら重合生成物（２×２５×２mmの方形）を取り出し、Ｉ
ＳＯ規格４０４９に準拠して曲げ強度を測定した。[Bending Strength] A sheet of polytetrafluoroethylene having a thickness of 2 mm was provided with a rectangular hole having a width of 2 mm and a length of 25 mm, a glass plate was applied to one side of the sheet, and the paste was filled into the hole from the opposite side. The surface was covered with cellophane, and light was irradiated for 90 seconds by a visible light irradiation device for polymerizing hard resin for crowns (Denta Color XS, manufactured by Kulzer). Then, the polymerized product (2 × 25 × 2 mm square) was taken out from the hole and I
Bending strength was measured according to SO standard 4049.
以上の測定結果を第１表に示す。Table 1 shows the above measurement results.
比較例 実施例と同様にして光増感剤を調整し、第１表に示した
割合で各種還元剤を添加し、光増感剤−還元剤系の光重
合性材料を調整した。以下実施例と同様の操作によって
ペーストを調整し、それらを用いて物性の測定を行っ
た。結果を第１表に示す。還元剤を添加していない比較
例１では、表層の僅か１mm厚さを除いて架橋しておら
ず、物性の測定ができなかった。Comparative Example A photosensitizer was prepared in the same manner as in Examples, and various reducing agents were added in the proportions shown in Table 1 to prepare a photosensitizer-reducing agent-based photopolymerizable material. The paste was prepared in the same manner as in the following examples, and the physical properties were measured using them. The results are shown in Table 1. In Comparative Example 1 in which the reducing agent was not added, physical properties could not be measured because the surface layer was not cross-linked except for a thickness of 1 mm.
［発明の効果］ 本発明の光重合性材料の光重合触媒を構成する還元剤
は、従来のアミン系還元剤に比較して、少量の添加で優
れた光重合性が得られ、また、得られた重合物の硬度、
機械的強度なども優れている。従って、歯科用コンポジ
ット樹脂、歯牙封止材、歯冠部および樹脂製義歯床など
歯科分野に広く用いることができる。さらに、アミン系
還元剤は人体に毒性を有するが、本発明の還元剤は人体
に無毒な還元剤である。[Effect of the invention] The reducing agent constituting the photopolymerization catalyst of the photopolymerizable material of the present invention can obtain excellent photopolymerizability with a small amount of addition as compared with the conventional amine-based reducing agent, and can be obtained. Hardness of the polymer,
It also has excellent mechanical strength. Therefore, it can be widely used in the dental field such as a dental composite resin, a tooth sealing material, a crown portion and a resin denture base. Further, although the amine-based reducing agent is toxic to the human body, the reducing agent of the present invention is a non-toxic reducing agent to the human body.
Claims (1)
還元剤からなる光重合触媒とから成る光重合性歯科材料
であって、光増感剤がカンファーキノンであり、還元剤
が一般式［Ｉ］、 （式中R1，R2は水素原子またはアルキル基） で表されるＮ−フェニルグリシンおよびそのアルキルエ
ステルから選ばれた還元剤であることを特徴とする光重
合性歯科材料。1. A photopolymerizable dental material comprising a radically polymerizable monomer and a photopolymerization catalyst comprising a photosensitizer and a reducing agent, wherein the photosensitizer is camphorquinone and the reducing agent is The general formula [I], A photopolymerizable dental material, which is a reducing agent selected from N-phenylglycine and its alkyl ester represented by the formula (wherein R 1 and R 2 are hydrogen atoms or alkyl groups).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61207785A JPH06689B2 (en) | 1986-09-05 | 1986-09-05 | Photopolymerizable dental material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61207785A JPH06689B2 (en) | 1986-09-05 | 1986-09-05 | Photopolymerizable dental material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6363605A JPS6363605A (en) | 1988-03-22 |
| JPH06689B2 true JPH06689B2 (en) | 1994-01-05 |
Family
ID=16545464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61207785A Expired - Lifetime JPH06689B2 (en) | 1986-09-05 | 1986-09-05 | Photopolymerizable dental material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06689B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5530038A (en) * | 1993-08-02 | 1996-06-25 | Sun Medical Co., Ltd. | Primer composition and curable composition |
| JP3665182B2 (en) * | 1997-07-22 | 2005-06-29 | 株式会社クラレ | Dental photopolymerizable composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE794482A (en) * | 1972-01-25 | 1973-07-24 | Du Pont | PHOTOPOLYMERISABLE COMPOSITIONS CONTAINING CYCLIC CIS- ALPHA -DICARBONYL COMPOUNDS AND SELECTED SENSITIZERS |
| JPS5410986A (en) * | 1977-06-25 | 1979-01-26 | Yoshimi Takada | Connection cable having independant shield skin |
| CA1137695A (en) * | 1979-06-18 | 1982-12-14 | Donald P. Specht | Photopolymerizable compositions featuring novel co-initiators |
| US4521550A (en) * | 1983-01-10 | 1985-06-04 | American Dental Association Health Foundation | Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates |
| JPS61144641A (en) * | 1984-12-18 | 1986-07-02 | Hitachi Chem Co Ltd | Photopolymerizable composition |
-
1986
- 1986-09-05 JP JP61207785A patent/JPH06689B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6363605A (en) | 1988-03-22 |
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