JP3604839B2 - Novel compound and adhesive composition using the same - Google Patents

Description

［上記式において、Ｒ _１ はＨ _２ Ｃ＝Ｃ（Ｒ _５ ）―を表し、Ｒ_２およびＲ_３は炭素数１〜４０の炭化水素基を表し、Ｒ _４ は水素または炭化水素基を表し、Ｒ_５は水素またはメチル基を表し、Ｘは―ＣＯＯ―、―ＯＯＣ―、―ＣＯＮＨ―、または―ＮＨＣＯ―を表し、ａ、ｂおよびｃは０または１を表す］。
【０００８】
また、本発明の新規化合物としては、下記一般式の化合物を用いることも好適である。
【化８】

［上記式において、Ｒ _１ はＨ _２ Ｃ＝Ｃ（Ｒ _８ ）―を表し、Ｒ_２、Ｒ_３およびＲ_４は炭素数１〜４０の炭化水素基を表し、Ｒ_５、Ｒ_６およびＲ_７は水素または炭化水素基を表し、Ｒ _８ は水素またはメチル基を表し、Ｘは―ＣＯＯ―、―ＯＯＣ―、―ＣＯＮＨ―、または―ＮＨＣＯ―を表し、ａ、ｂ、ｃおよびｄは０または１を表す］。
なお、本発明でいう有機基とは、
（イ）炭化水素基［ただし、水素がハロゲン、水酸基、カルボキシル基、スルフォン酸基、アミノ基、チイラン基、リン酸基などで置換されてもよい］
または、
（ロ）少なくとも１個の上記炭化水素基が、少なくとも１個の以下に示す結合部−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−ＮＨ−、単独またはそれらが互いに接合して複合化した結合部によって連結されて構成された基を意味する。
【０００９】
上記一般式で示される新規化合物中、本発明で特に好ましく用いられる化合物としては、下記一般式
【化１０】

［上記式においてＲ_１は水素またはメチル基を表し、ｍおよびｎは０〜４０を表す］
で表される（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸が挙げられる。
【００１０】
本発明の新規化合物は、通常の方法により合成することができる。例えば一般式
【化１１】

［上記式においてＲ_１は水素またはメチル基を表し、ｍおよびｎは０〜４０を表す］
で表される（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸の合成方法としては、例えばオキシ塩化リンまたはオキシ臭化リンにヒドロキシアルキル（メタ）アクリレートと２ーヒドロキシアルキルチイランをベンゼン、エーテル、またはクロロホルム等の溶媒中でトリエチルアミンまたはピリジン等の脱塩酸化剤の存在下に反応させてから水で加水分解して目的の（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸を得る方法（この２種類のアルコールをオキシ塩化リンと反応させる順序はどちらを先に反応させてもよい）、上述の反応において２ーヒドロキシアルキルチイランの代わりに２ーヒドロキシアルキルオキシランを用いて、リン酸水素ジエステルとした後、エポキシ基をチオ尿素またはチオシアン酸塩と反応させてチイランとすることにより、目的の（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸を得る方法、アルケノールとヒドロキシアルキル（メタ）アクリレートをオキシ塩化リンまたはオキシ臭化リンと反応後、加水分解して得たリン酸水素ジエステル誘導体を過酸化水素、過酢酸または過安息香酸等で酸化することにより得られたエポキシ誘導体をさらにチオ尿素またはチオシアン酸塩と反応させてチイラン誘導体とすることにより、目的の（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸を得る方法、およびアルケノールとヒドロキシアルキル（メタ）アクリレートをオキシ塩化リンまたはオキシ臭化リンと反応後、加水分解して得たリン酸水素ジエステル誘導体のアルケンを塩化イオウと反応後、硫化ナトリウム等で還元してチイラン誘導体とすることにより、目的の（メタ）アクリロイルオキシアルキルエピチオアルキルリン酸を得る方法を挙げることができる。また（メタ）アクリロイルオキシアルキルー２，３ーエピチオプロピルリン酸の合成方法としては、例えばリン酸のモノ（メタ）アクリロイルオキシアルキルエステルを通法によりモノアルカリ塩とし、これをエピクロルヒドリンと反応させ、（メタ）アクリロイルオキシアルキルー２ーヒドロキシー３ークロロプロピルリン酸のアルカリ塩を生成し、さらにアルカリで閉環させ、（メタ）アクリロイルオキシアルキルー２，３ーエポキシプロピルリン酸のアルカリ塩とし、これをチオ尿素またはチオシアン酸塩と反応させてチイラン誘導体とした後、酸で中和することにより目的の（メタ）アクリロイルオキシアルキルー２，３ーエピチオプロピルリン酸を得る方法を挙げることができる。ただし、本発明の新規化合物の合成は上述の合成方法に限定されるものではない。
【００１１】
本発明の接着剤組成物は、上記の新規化合物を用い、下記に示す（１）または（２）のように調製される。
【００１２】
（１）上記新規化合物を溶剤に溶解してプライマーとして使用する。溶剤としては沸点２５０℃以下の揮発性有機溶剤（メタノール、エタノール、アセトン、酢酸エチル、塩化メチレン、トルエン等）、水またはこれらの混合物が用いられる。新規化合物の濃度は０．０００１〜５０重量％、好ましくは０．００１〜１０重量％に溶解する。さらに必要に応じ、後述する重合開始剤、共重合性単量体を加えてもよい。得られたプライマーを被着体表面に塗布し、さらにその上に通常用いられる接着剤またはコンポジットレジンを塗布し、接着する。また、金属表面に塗布する場合には、プライマー塗布面を溶剤等で洗浄して過剰の接着剤組成物を除去してもよい。
【００１３】
（２）上記新規化合物を共重合性のある単量体に溶解して接着剤として使用する。使用する共重合性単量体としては、（メタ）アクリル酸エステルが好ましく、具体的には、メチルメタクリレート、トリエチレングリコールジメタクリレート、２−ヒドロキシエチルメタクリレ−ト、２，２−ビス［４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）フェニル］プロパン（Ｂｉｓ−ＧＭＡと称する）、ペンタエリスリト−ルテトラアクリレ−ト等が挙げられ、また、他の接着効果のある共重合性単量体組成物を併用してもよい。併用する接着効果のある共重合性単量体組成物としては、例えば、４−メタクリロイルオキシエチルトリメリット酸無水物、２−メタクリロイルオキシエチルフェニルハイドロジエンホスフェ−ト、１０−メタクリロイルオキシデシルジハイドロジエンホスフェ−ト、３−メタクリロイルオキシプロピルトリメトキシシランを挙げることができる。新規化合物の濃度は０．００５〜５０重量％、好ましくは０．１〜２０重量％で共重合性単量体に溶解する。さらに、該接着剤組成物には、通常、重合開始剤を加える。かかる重合開始剤としては、過酸化ベンゾイル−芳香族第３級アミン系、トリブチルボラン、芳香族スルフィン酸（または、その塩）−芳香族アミン系などが挙げられ、さらに、カンファーキノン、ベンゾインエチルエ−テル等の光重合開始剤を挙げることができる。また、該接着剤組成物には、必要に応じ、フィラー、溶剤等を加えてもよい。
【００１４】
本発明の新規化合物において、分子中に含まれるチイラン基は特に貴金属と有効に接着し、リン酸基は特に非貴金属と有効に接着する。また、オレフィン性の二重結合は他の不飽和結合をもつ物質と結合する。本発明の新規化合物自体が共重合が可能であり、より強い接着力を得ることができる。さらに、リン酸基およびチイラン基はアミノ基および水酸基と結合が可能であり、例えば歯質や骨等と有効に接着する。
【００１５】
【実施例】
次に、本発明を実施例により具体的に説明するが、本発明はその要旨を越えない限り下記の実施例に限定されるものではない。
【００１６】
実施例１
（６ー（メタクリロイルオキシ）ヘキシルー３，４ーエピチオブチルリン酸の調製および確認）
２００ｍｌの三口フラスコにメタクリル酸（２１．５ｇ）、ヘキサメチレングリコール（５９．１ｇ）、ｐ−トルエンスルホン酸（２．９ｇ）およびｐ−ヒドロキノン（１．０ｇ）を秤取し、浴槽温度９０℃にて酸素ガスをバブルさせながら水流ポンプで１５０ｍｍＨｇ程度にして生成する水を留去した。徐々に浴槽温度および減圧度を上げて、１０時間後に浴槽温度１２０℃、減圧度４０ｍｍＨｇにて３０分間反応させて終了した。反応混合物を５００ｍ１のベンゼンに加えてベンゼン可溶成分を抽出した。ベンゼン溶液を５％水酸化ナトリウム水溶液で洗浄後、水で３回洗浄して酸を除去し、無水硫酸ナトリウムを加えて乾燥させた。ベンゼンを留去すると３５．２ｇの褐色の液体が得られた。１３０ｇのワコーゲルＣ−３００（和光純薬工業製）をベンゼンに分散させて詰めたカラムに粗精製物をチャージして、ベンゼンを展開溶媒として分離精製した。溶出液は紫外可視検出器でモニター（波長：２７０ｎｍ）し、各ピーク毎に溶出液を分け、濃縮してＩＲおよびＮＭＲスペクトルにより成分を確認した。６ーヒドロキシヘキシルメタクリレートが２０．２ｇの淡黄色液体として得られた（収率：４３．３％）。
【００１７】
５００ｍｌのクロロホルムに３−ブテン−１−オール（１１．４ｇ）を溶解させ、４℃に冷却してからｍ−クロロ過安息香酸（純度８０％，３４．１ｇ）を加えて撹拌して溶解した。４℃で５時間反応させ、室温でさらに３時間反応させた後、０℃に冷却して析出結晶を濾別した。濾液を濃縮後、２００ｍ１のベンゼンを加えて再び４℃に冷却して析出結晶を濾別した。濾液のベンゼン溶液をイオン交換樹脂（アンバーリストＡ−２１，オルガノ製）を充填したカラムに通して、ｍ−クロロ過安息香酸を除去した。ベンゼン溶液を濃縮後、淡黄色の液体として３，４−エポキシ−１−ブタノール１２．２ｇが得られた（収率：８７．２％）。
【００１８】
１１０ｍｌの脱水メタノール中に３，４−エポキシ−１−ブタノール（１２．２ｇ）を溶解させ、４℃に冷却してからチオ尿素（１３．５ｇ）を加えて撹拌して溶解させた。４℃で３時間、室温で１０時間撹拌しながら反応させた。反応終了後、メタノールを留去し、１００ｍｌのベンゼンを加えて十分に撹拌してから４℃に冷却して固体を析出させた。析出固体を濾別後、ベンゼン溶液を５ｇのシリカゲル（ワコーゲルＣ−３００，和光純薬工業製）をベンゼンで充填したカラムに通してチオ尿素を除去した。溶出液を濃縮後、淡黄色の液体として３，４−エピチオ−１−ブタノール７．５ｇが得られた（収率：５１．６％）。
【００１９】
１００ｍｌの三口フラスコにオキシ塩化リン（４．９ｇ）と脱水精製クロロホルム（２０ｍｌ）を加え、別々の滴下ロートにそれぞれ６−ヒドロキシヘキシルメタクリレート（６．０ｇ）に脱水精製クロロホルム（５ｍｌ）を加えた溶液およびトリエチルアミン（３．３ｇ）に脱水精製クロロホルム（５ｍｌ）を加えた溶液を秤取し、０℃に冷却してから、２つの滴下ロートから６−ヒドロキシヘキシルメタクリレートとトリエチルアミンを３０分かけて撹拌しながら同時に滴下した。滴下終了後３０分間０℃で撹拌してから、新たに２つの滴下ロートにそれぞれ３，４−エピチオ−１−ブタノール（３．４ｇ）に脱水精製クロロホルム（５ｍｌ）を加えた溶液およびトリエチルアミン（３．３ｇ）に脱水精製クロロホルム（５ｍｌ）を加えた溶液を秤取し、滴下ロートを三口フラスコに装着して、同様に０℃にて撹拌しながら３０分間で同時に滴下させた。滴下終了後１時間０℃で撹拌してから、室温に戻して２時間撹拌させた。再び、０℃に冷却して水（２０ｍｌ）とトリエチルアミン（３．３ｇ）を反応溶液に加えて３０分間撹拌しながら反応させた。反応混合物にクロロホルム（２００ｍｌ）を加えて分液ロートに移し、水層を分離してから、４０ｍｌの水で洗浄、４℃に冷却して１Ｎの塩酸（４０ｍｌ）で洗浄、さらに４０ｍｌの水で４回洗浄後、無水硫酸ナトリウムをクロロホルム溶液に加えて乾燥させた。クロロホルムを留去後、橙色の液体１２．０ｇが得られた。１３０ｇのシリカゲル（ワコーゲルＣ−３００，和光純薬工業製）をクロロホルムに分散させて詰めたカラムに粗精製物をチャージして、クロロホルム、３重量％メタノール添加クロロホルム、５重量％メタノール添加クロロホルムの順に展開溶媒の極性を増大させて分離精製した。溶出液は紫外可視検出器でモニター（波長：２５４ｎｍ）し、各ピーク毎に溶出液を分け、濃縮してＩＲおよびＮＭＲスペクトルにより成分を確認した。該当溶出液を濃縮、減圧乾燥後、無色の液体として６−（メタクリロイルオキシ）ヘキシル−３，４−エピチオブチルリン酸２．７ｇが得られた（収率：２３．４％）。
【００２０】
６−（メタクリロイルオキシ）ヘキシル−３，４−エピチオブチルリン酸のＩＲおよびＮＭＲスペクトルのデータを次に示す。なお、^１Ｈ−ＮＭＲのａ〜ｏは図１に示すａ〜ｏ水素原子に対応し、^１３Ｃ−ＮＭＲのａ〜ｎは図２に示すａ〜ｎの炭素原子に対応している。
ＩＲスペクトル（ｃｍ^−１）：
Ｐ−Ｏ−Ｃ １０２０，Ｃ−Ｏ−Ｃ １１６６，Ｃ＝Ｃ １６３２，Ｃ＝Ｏ １７１２
^１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ_３）δｐｐｍ（Ｈ数）：
ａ ５．５５（１Ｈ），ｂ ６．０９（１Ｈ），ｃ １．９４（１Ｈ），ｄ＋ｉ＋ｋ ３．９４−４．２５（６Ｈ）．ｅ＋ｈ＋ｌ １．６８（５Ｈ），ｆ＋ｇ１．４２（４Ｈ），ｊ ９．９８（１Ｈ），ｌ ２．３１（１Ｈ），ｍ ３．００（１Ｈ），ｎ ２．５６（１Ｈ），ｏ ２．２１（１Ｈ）
^１３Ｃ−ＮＭＲスペクトル：
ａ １２５．２０，ｂ １３６．４４，ｃ １８．２７，ｄ １６７．４７，ｅ６４．５１，ｆ ２８．４７，ｇ＋ｈ ２５．１０とｃａ２５．５２，ｉ ３０．０２，ｊ ６７．６６，ｋ ６６．８５，ｌ ３７．０２，ｍ ３１．７８，ｎ ｃａ２５．５２
【００２１】
実施例２
（接着剤組成物の調製および接着強度試験）
接着剤組成物としては６―（メタクリロイルオキシ）ヘキシル―３，４―エピチオブチルリン酸の１ｍｏｌ％（接着剤組成物１）および６―（メタクリロイルオキシ）ヘキシル―３，４―エピチオブチルリン酸の０．０１ｍｏｌ％エタノール溶液（接着剤組成物２）を調製した。それぞれの接着剤組成物について以下の試験を実施した。
次に示す貴金属合金および非貴金属合金を被着体金属とし、それぞれの金属について、後部に引張試験用の治具に接続するための雄ネジを付与した直径５ｍｍの円柱状の試験片を１０個ずつ調製した。貴金属合金［金合金：ＣａｓｔｉｎｇＧｏｌｄ Ｍ．Ｃ．Ｔｙｐｅ ＩＶ（ジーシー製）、金銀パラジウム合金：Ｃａｓｔｗｅｌｌ Ｍ．Ｃ．（ジーシー製）および銀合金：Ｓｕｎｓｉｌｖｅｒ Ｃ．Ｂ．（三金工業製）］および非貴金属合金［コバルトクロム合金：Ｄｕｒａｌｌｉｕｍ ＪＤ（Ｊｅｌｅｎｋｏ製）、ニッケルクロム合金：ＳＢ ｂｏｎｄｌｏｙ Ｉ（トーワ技研製）およびチタン：ＴＩ―４５２５９４（ニラコ製）］。各試験片の前部表面（被着面）を洗浄乾燥後、ラッピングフィルム＃４０００により鏡面研磨した。
【００２２】
接着剤組成物５μｌを各金属試験片の被着面に塗布し、１日放置した。接着剤組成物１についてはさらにアセトンで被着面を洗浄（余剰モノマーの除去）風乾し、接着強度測定用の試料を調製した。同一金属を２つ１組とし、トリブチルボラン部分酸化物（ＴＢＢＯ）を含むメチルメタクリレート／ポリメチルメタクリレートからなるペースト（ペースト Ｉ）および０．５重量％のＮ，Ｎ−ジヒドロキシエチル−ｐ−トルイジンを含むメチルメタクリレート／１．０重量％の過酸化ベンゾイルを含むポリメチルメタクリレートからなるペースト（ペースト
ＩＩ）のそれぞれのペーストを用いて筆積み法により被着面と被着面を突き合わせ接着し、余剰のペーストは除去した。室温で１時間硬化させた後に、４℃と６０℃との水中で１分間ずつ交互に、２０００回の熱サイクルを繰り返した後、２ｍｍ／ｍｉｎのクロスヘッド速度で引張試験を行った。接着剤組成物１の結果を表１に、接着剤組成物２の結果を表２に示した。
【００２３】
【表１】

【００２４】
【表２】

【００２５】
【発明の効果】
本発明の新規化合物およびこれを用いた接着剤組成物は、非貴金属および貴金属の両金属類に対して強い接着力を有するものである。
【図面の簡単な説明】
【図１】^１Ｈ−ＮＭＲスペクトルの水素原子の位置を示す図である。
【図２】^１３Ｃ−ＮＭＲスペクトルの炭素原子の位置を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel compound and an adhesive composition using the same. The novel compounds of the present invention are useful in the field of adhesives, and especially useful in the field of dentistry. The term "adhesive" in the present invention includes an adherend surface treating agent used in bonding an adherend to another material.
[0002]
[Prior art]
Organic for both metals such as precious metals (gold, silver, palladium and precious metal alloys containing these as main components) and non-precious metals (nickel, chromium, titanium, iron, copper and non-precious metal alloys containing these as main components) Strong bonding of materials is widely demanded in various fields. Particularly in the field of dentistry, various metal alloys are used for crowns, inlays, denture bases and the like irrespective of precious metals and non-precious metals, and an adhesive effective for these various metal alloys has been demanded. However, heretofore, such an adhesive has not been found. As a non-precious metal adhesive, a phosphate group-containing compound has been proposed in, for example, JP-A-52-113089 and JP-A-58-21607, and is widely used in general clinical practice. However, it is generally known that this compound has high adhesion to non-noble metals, but hardly adheres to noble metals.
[0003]
On the other hand, as a noble metal adhesive, a sulfur compound has been proposed. For example, a compound containing a triazinethiol group (JP-A-62-292744), a compound containing a mercapto group or a polysulfide group (JP-A-63-225674), a compound containing a triazinedithione derivative (JP-A-64-83254), thioline Examples include an acid group-containing compound (Japanese Patent Application Laid-Open No. 64-90276) and a thiophosphoric acid dichloride group-containing compound (Japanese Patent Application Laid-Open No. 5-117595). . However, these compounds are still questionable in terms of storage stability or long-term adhesion durability, and still remain uneasy in actual clinical use.
[0004]
In addition, the present inventors have proposed a thiirane group-containing compound (Japanese Patent Application No. 7-100261) to solve such a problem. In other words, it has been confirmed that the thiirane group-containing compound has a high adhesive force to a noble metal, and also has storage stability and long-term adhesion durability. However, questions remain regarding the adhesion of any of the above compounds to non-noble metals.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described circumstances, and has as its object to provide a novel compound having excellent adhesion performance to both non-noble metals and precious metals, and an object of providing an adhesive composition using the same. And
[0006]
[Means for Solving the Problems]
An object of the present invention is to provide a novel compound having at least one or more thiirane groups, at least one or more phosphate groups and at least one or more olefinic double bonds in the same molecule at the same time, and an adhesive composition using the same. Is achieved by
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The novel compound of the present invention is a compound having at least one or more thiirane groups, at least one or more phosphate groups, and at least one or more olefinic double bonds in the same molecule at the same time. Although various compounds can be used, it is preferable to use a compound represented by the following general formula.
Embedded image

[In the above formula, R ₁ represents H ₂ C ＝ C (R ₅ ) —, R ₂ and R ₃ represent a hydrocarbon group having 1 to 40 carbon atoms, R ₄ represents hydrogen or a hydrocarbon group, R ₅ represents hydrogen or a methyl group, X represents —COO—, —OOC—, —CONH—, or —NHCO—, and a, b, and c represent 0 or 1].
[0008]
It is also preferable to use a compound represented by the following general formula as the novel compound of the present invention.
Embedded image

[In the above formula, R ₁ represents H ₂ C ＝ C (R ₈ ) — , R ₂ , R ₃ and R ₄ represent a hydrocarbon group having 1 to 40 carbon atoms, and R ₅ , R ₆ and R ₇ Represents hydrogen or a hydrocarbon group, R ₈ represents hydrogen or a methyl group, X represents —COO—, —OOC—, —CONH—, or —NHCO—, a, b, c, and d represent 0 or 1].
Incidentally, the organic group referred to in the present invention,
(A) Hydrocarbon group [however, hydrogen may be substituted by halogen, hydroxyl group, carboxyl group, sulfonic acid group, amino group, thiirane group, phosphate group, etc.]
Or
(B) at least one of the above hydrocarbon groups has at least one of the following bonding parts -O-, -CO-, -S-, -SO-, -NH-, alone or in combination with each other; It means a group constituted by being connected by a complexed bonding part.
[0009]
Among the novel compounds represented by the above general formula, compounds particularly preferably used in the present invention include compounds represented by the following general formula:

[In the above formula, R ₁ represents hydrogen or a methyl group, and m and n represent 0 to 40]
(Meth) acryloyloxyalkylepithioalkylphosphoric acid represented by the following formula:
[0010]
The novel compound of the present invention can be synthesized by a usual method. For example, the general formula

[In the above formula, R ₁ represents hydrogen or a methyl group, and m and n represent 0 to 40]
As a method for synthesizing (meth) acryloyloxyalkylepithioalkylphosphoric acid represented by the following formula, for example, phosphorus oxychloride or phosphorus oxybromide is added to hydroxyalkyl (meth) acrylate and 2-hydroxyalkylthiirane in benzene, ether, or chloroform. Reaction in a solvent such as triethylamine or pyridine in the presence of a dehydrochlorinating agent and then hydrolysis with water to obtain the desired (meth) acryloyloxyalkylepithioalkylphosphoric acid (the two alcohols May be reacted with phosphorus oxychloride in either order). In the above reaction, 2-hydroxyalkyl oxirane is used instead of 2-hydroxyalkyl thiirane to form a hydrogen phosphate diester, and then epoxy Thiourea or thiocyanate group A method for obtaining the desired (meth) acryloyloxyalkylepithioalkylphosphoric acid by reacting with thiirane; hydrolyzing an alkenol with a hydroxyalkyl (meth) acrylate after reacting it with phosphorus oxychloride or phosphorus oxybromide; The epoxy derivative obtained by oxidizing the hydrogen phosphate diester derivative obtained with the above with hydrogen peroxide, peracetic acid, perbenzoic acid, or the like, is further reacted with thiourea or thiocyanate to form a thiirane derivative. Of (meth) acryloyloxyalkylepithioalkyl phosphoric acid, and reaction of alkenol with hydroxyalkyl (meth) acrylate with phosphorus oxychloride or phosphorus oxybromide, followed by hydrolysis to obtain a hydrogen phosphate diester derivative After reacting the alkene with sulfur chloride, With thiirane derivative is reduced with sodium or the like, can be mentioned a method of obtaining the intended (meth) acryloyloxy alkyl epithiopropyl alkyl phosphates. As a method for synthesizing (meth) acryloyloxyalkyl-2,3-epithiopropylphosphoric acid, for example, a mono (meth) acryloyloxyalkylester of phosphoric acid is converted into a mono-alkali salt by a conventional method, and this is reacted with epichlorohydrin. To produce an alkali salt of (meth) acryloyloxyalkyl-2-hydroxy-3-chloropropyl phosphoric acid, and further ring-closing with alkali to form an alkali salt of (meth) acryloyloxyalkyl-2,3-epoxypropyl phosphoric acid. Is reacted with thiourea or thiocyanate to form a thiirane derivative, and then neutralized with an acid to obtain the desired (meth) acryloyloxyalkyl-2,3-epithiopropyl phosphoric acid. . However, the synthesis of the novel compound of the present invention is not limited to the above synthesis method.
[0011]
The adhesive composition of the present invention is prepared using the above novel compound as shown in the following (1) or (2).
[0012]
(1) The novel compound is dissolved in a solvent and used as a primer. As the solvent, a volatile organic solvent having a boiling point of 250 ° C. or lower (methanol, ethanol, acetone, ethyl acetate, methylene chloride, toluene, or the like), water, or a mixture thereof is used. The new compound is dissolved in a concentration of 0.0001 to 50% by weight, preferably 0.001 to 10% by weight. If necessary, a polymerization initiator and a copolymerizable monomer described below may be added. The primer thus obtained is applied to the surface of the adherend, and a commonly used adhesive or composite resin is applied thereon and adhered. In the case of coating on a metal surface, the primer-coated surface may be washed with a solvent or the like to remove excess adhesive composition.
[0013]
(2) The novel compound is dissolved in a copolymerizable monomer and used as an adhesive. As the copolymerizable monomer to be used, (meth) acrylic acid ester is preferable. Specifically, methyl methacrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, 2,2-bis [4 -(3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (referred to as Bis-GMA), pentaerythritol tetraacrylate, and other copolymerizable monomer compositions having an adhesive effect You may use things together. Examples of the copolymerizable monomer composition having an adhesive effect to be used in combination include, for example, 4-methacryloyloxyethyl trimellitic anhydride, 2-methacryloyloxyethyl phenylhydrodiene phosphate, and 10-methacryloyloxydecyl dihydrogen. Examples thereof include diene phosphate and 3-methacryloyloxypropyltrimethoxysilane. The new compound is dissolved in the copolymerizable monomer at a concentration of 0.005 to 50% by weight, preferably 0.1 to 20% by weight. Further, a polymerization initiator is usually added to the adhesive composition. Examples of such a polymerization initiator include benzoyl peroxide-aromatic tertiary amine-based, tributylborane, aromatic sulfinic acid (or a salt thereof) -aromatic amine-based, and further, camphorquinone, benzoinethyl ether -Photopolymerization initiators such as tellurium. Further, a filler, a solvent, and the like may be added to the adhesive composition as needed.
[0014]
In the novel compounds of the present invention, the thiirane groups contained in the molecule adhere particularly effectively to noble metals, and the phosphate groups adhere particularly effectively to non-noble metals. Further, the olefinic double bond is bonded to a substance having another unsaturated bond. The novel compound of the present invention itself can be copolymerized, and a stronger adhesive force can be obtained. Furthermore, the phosphate group and the thiirane group can bond to the amino group and the hydroxyl group, and effectively adhere to, for example, tooth material and bone.
[0015]
【Example】
Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
[0016]
Example 1
(Preparation and confirmation of 6- (methacryloyloxy) hexyl-3,4-epithiobutyl phosphate)
Methacrylic acid (21.5 g), hexamethylene glycol (59.1 g), p-toluenesulfonic acid (2.9 g) and p-hydroquinone (1.0 g) were weighed into a 200 ml three-necked flask, and the bath temperature was 90 ° C. The water produced was distilled off by bubbling oxygen gas at about 150 mmHg with a water flow pump. The bath temperature and the degree of vacuum were gradually raised, and after 10 hours, the reaction was completed at a bath temperature of 120 ° C. and a degree of vacuum of 40 mmHg for 30 minutes to complete the reaction. The reaction mixture was added to 500 ml of benzene to extract a benzene-soluble component. The benzene solution was washed with a 5% aqueous solution of sodium hydroxide, then washed three times with water to remove the acid, and dried over anhydrous sodium sulfate. When benzene was distilled off, 35.2 g of a brown liquid was obtained. The crude product was charged into a column packed with 130 g of Wakogel C-300 (manufactured by Wako Pure Chemical Industries) dispersed in benzene, and separated and purified using benzene as a developing solvent. The eluate was monitored with an ultraviolet-visible detector (wavelength: 270 nm), the eluate was separated for each peak, concentrated, and the components were confirmed by IR and NMR spectra. 6-Hydroxyhexyl methacrylate was obtained as a light yellow liquid (20.2 g, yield: 43.3%).
[0017]
3-buten-1-ol (11.4 g) was dissolved in 500 ml of chloroform, cooled to 4 ° C., m-chloroperbenzoic acid (purity 80%, 34.1 g) was added, and the mixture was stirred and dissolved. . After reacting at 4 ° C. for 5 hours and at room temperature for further 3 hours, the mixture was cooled to 0 ° C. and the precipitated crystals were separated by filtration. After concentrating the filtrate, 200 ml of benzene was added, and the mixture was cooled again to 4 ° C., and the precipitated crystals were separated by filtration. The benzene solution of the filtrate was passed through a column filled with an ion exchange resin (Amberlyst A-21, manufactured by Organo) to remove m-chloroperbenzoic acid. After concentrating the benzene solution, 12.2 g of 3,4-epoxy-1-butanol was obtained as a pale yellow liquid (yield: 87.2%).
[0018]
3,4-Epoxy-1-butanol (12.2 g) was dissolved in 110 ml of dehydrated methanol, cooled to 4 ° C., and thiourea (13.5 g) was added and stirred to dissolve. The reaction was carried out with stirring at 4 ° C. for 3 hours and at room temperature for 10 hours. After completion of the reaction, methanol was distilled off, 100 ml of benzene was added, and the mixture was sufficiently stirred, and then cooled to 4 ° C. to precipitate a solid. After separating the precipitated solid by filtration, the benzene solution was passed through a column filled with 5 g of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries) with benzene to remove thiourea. After concentrating the eluate, 7.5 g of 3,4-epithio-1-butanol was obtained as a pale yellow liquid (yield: 51.6%).
[0019]
Phosphorus oxychloride (4.9 g) and dehydrated purified chloroform (20 ml) were added to a 100 ml three-necked flask, and 6-hydroxyhexyl methacrylate (6.0 g) and dehydrated purified chloroform (5 ml) were added to separate dropping funnels. And a solution obtained by adding dehydrated and purified chloroform (5 ml) to triethylamine (3.3 g), cooled to 0 ° C., and stirred 6-hydroxyhexyl methacrylate and triethylamine from two dropping funnels for 30 minutes. While simultaneously dropping. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 30 minutes, and a solution of 3,4-epithio-1-butanol (3.4 g) and purified dehydrated chloroform (5 ml) was added to two new dropping funnels and triethylamine (3. 0.3 g) and dehydrated purified chloroform (5 ml) added thereto were weighed, a dropping funnel was attached to a three-necked flask, and the mixture was simultaneously dropped at 0 ° C. for 30 minutes while stirring. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 1 hour, then returned to room temperature and stirred for 2 hours. Again, the mixture was cooled to 0 ° C., water (20 ml) and triethylamine (3.3 g) were added to the reaction solution, and reacted with stirring for 30 minutes. Chloroform (200 ml) was added to the reaction mixture, which was transferred to a separating funnel. The aqueous layer was separated, washed with 40 ml of water, cooled to 4 ° C, washed with 1N hydrochloric acid (40 ml), and further washed with 40 ml of water. After washing four times, anhydrous sodium sulfate was added to the chloroform solution and dried. After the chloroform was distilled off, 12.0 g of an orange liquid was obtained. The crude product was charged into a column packed with 130 g of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries) dispersed in chloroform, and chloroform, chloroform with 3 wt% methanol, and chloroform with 5 wt% methanol were added in this order. Separation and purification were performed by increasing the polarity of the developing solvent. The eluate was monitored with an ultraviolet-visible detector (wavelength: 254 nm), the eluate was separated for each peak, concentrated, and the components were confirmed by IR and NMR spectra. After the corresponding eluate was concentrated and dried under reduced pressure, 2.7 g of 6- (methacryloyloxy) hexyl-3,4-epithiobutyl phosphate was obtained as a colorless liquid (yield: 23.4%).
[0020]
The data of the IR and NMR spectra of 6- (methacryloyloxy) hexyl-3,4-epithiobutylphosphate are shown below. In addition, a to o of ¹ H-NMR correspond to a to o hydrogen atoms shown in FIG. 1, and a to n of ¹³ C-NMR correspond to a to n carbon atoms shown in FIG. 2.
IR spectrum (cm ^-1 ):
POC 1020, COC 1166, C = C 1632, C = O 1712
¹ H-NMR spectrum (CDCl ₃ ) δ ppm (H number):
a 5.55 (1H), b 6.09 (1H), c 1.94 (1H), d + i + k 3.94-4.25 (6H). e + h + l 1.68 (5H), f + g 1.42 (4H), j 9.98 (1H), l 2.31 (1H), m 3.00 (1H), n 2.56 (1H), o2. 21 (1H)
¹³ C-NMR spectrum:
a 125.20, b 136.44, c 18.27, d 167.47, e64.51, f 28.47, g + h 25.10 and ca 25.52, i 30.02, j 67.66, k 66 .85, l 37.02, m 31.78, n ca 25.52
[0021]
Example 2
(Preparation of adhesive composition and adhesive strength test)
As the adhesive composition, 1-mol% of 6- (methacryloyloxy) hexyl-3,4-epithiobutylphosphoric acid (adhesive composition 1) and 6- (methacryloyloxy) hexyl-3,4-epithiobutylphosphate A 0.01 mol% solution of an acid in ethanol (adhesive composition 2) was prepared. The following tests were performed on each adhesive composition.
The following noble metal alloys and non-noble metal alloys were used as adherend metals, and for each metal, 10 cylindrical test pieces having a diameter of 5 mm and provided with male screws at the rear for connecting to a jig for a tensile test were used. Each was prepared. Noble metal alloy [gold alloy: Casting Gold M. C. Type IV (manufactured by GC), gold-silver palladium alloy: Castwell M. C. (Manufactured by GC) and a silver alloy: Sunsilver C.I. B. (Manufactured by Sankin Industries)] and non-precious metal alloys [cobalt chromium alloy: Durallium JD (manufactured by Jelenko), nickel chromium alloy: SB bondloy I (manufactured by Towa Giken) and titanium: TI-452594 (manufactured by Nilaco)]. After washing and drying the front surface (coated surface) of each test piece, it was mirror-polished with a wrapping film # 4000.
[0022]
5 μl of the adhesive composition was applied to the adhered surface of each metal test piece and allowed to stand for one day. The adhesive surface of the adhesive composition 1 was further washed with acetone (removing excess monomer) and air-dried to prepare a sample for measuring adhesive strength. The same metal is used as a pair, and a paste composed of methyl methacrylate / polymethyl methacrylate containing tributyl borane partial oxide (TBBO) (paste I) and 0.5% by weight of N, N-dihydroxyethyl-p-toluidine are used. Using a paste (paste II) composed of a polymethyl methacrylate containing 1.0% by weight of benzoyl peroxide containing methyl methacrylate, the adhered surface and the adhered surface were butt-adhered to each other by a brushing method, and the excess The paste was removed. After curing at room temperature for 1 hour, the heat cycle was repeated 2000 times alternately in water at 4 ° C. and 60 ° C. for 1 minute, and then a tensile test was performed at a crosshead speed of 2 mm / min. Table 1 shows the results of the adhesive composition 1 and Table 2 shows the results of the adhesive composition 2.
[0023]
[Table 1]

[0024]
[Table 2]

[0025]
【The invention's effect】
The novel compound of the present invention and the adhesive composition using the same have strong adhesion to both non-precious metals and precious metals.
[Brief description of the drawings]
FIG. 1 is a diagram showing positions of hydrogen atoms in a ¹ H-NMR spectrum.
FIG. 2 is a diagram showing positions of carbon atoms in a ¹³ C-NMR spectrum.

Claims (4)

A novel compound having at least one or more thiirane groups, at least one or more phosphate groups, and at least one or more olefinic double bonds in the same molecule at the same time, having the general formula

[In the above formula, R ₁ represents H ₂ C ＝ C (R ₅ ) —, R ₂ and R ₃ represent a hydrocarbon group having 1 to 40 carbon atoms, R ₄ represents hydrogen or a hydrocarbon group, R ₅ represents hydrogen or a methyl group, X is -COO -, - OOC -, - CONH-, or an -NHCO-, novel compounds represented by a, b and c represents 0 or 1]. A novel compound having at least one or more thiirane groups, at least one or more phosphate groups, and at least one or more olefinic double bonds in the same molecule at the same time, having the general formula

[In the above formula, R ₁ represents H ₂ C ＝ C (R ₈ ) — , R ₂ , R ₃ and R ₄ represent a hydrocarbon group having 1 to 40 carbon atoms, and R ₅ , R ₆ and R ₇ Represents hydrogen or a hydrocarbon group, R ₈ represents hydrogen or a methyl group, X represents —COO—, —OOC—, —CONH—, or —NHCO—, a, b, c, and d represent 0 or novel compounds represented by representing the 1. The new compound has the general formula

The novel compound according to claim 1, wherein R ₁ represents hydrogen or a methyl group, and m and n represent 0 to 40. An adhesive composition comprising the novel compound according to claim 1 as one of the components.

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