JPH0468007A - New silicone-modified acrylic resin, its production and dental adhesive prepared by using said resin - Google Patents
New silicone-modified acrylic resin, its production and dental adhesive prepared by using said resinInfo
- Publication number
- JPH0468007A JPH0468007A JP2180931A JP18093190A JPH0468007A JP H0468007 A JPH0468007 A JP H0468007A JP 2180931 A JP2180931 A JP 2180931A JP 18093190 A JP18093190 A JP 18093190A JP H0468007 A JPH0468007 A JP H0468007A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acrylic resin
- silicone
- modified acrylic
- resin
- 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.)
- Granted
Links
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 24
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003479 dental cement Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011347 resin Substances 0.000 title abstract description 6
- 229920005989 resin Polymers 0.000 title abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 17
- -1 silane compound Chemical class 0.000 abstract description 17
- 229920002379 silicone rubber Polymers 0.000 abstract description 13
- 239000004945 silicone rubber Substances 0.000 abstract description 13
- 229910000077 silane Inorganic materials 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 11
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 4
- 210000000214 mouth Anatomy 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- INTFCWANRCGCRZ-UHFFFAOYSA-N 3-tris(dimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound C[SiH](C)O[Si](O[SiH](C)C)(O[SiH](C)C)CCCOC(=O)C(C)=C INTFCWANRCGCRZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- KWISWUFGPUHDRY-UHFFFAOYSA-N 1-Chloro-2-methylpropene Chemical compound CC(C)=CCl KWISWUFGPUHDRY-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 210000001909 alveolar process Anatomy 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 210000001847 jaw Anatomy 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000004877 mucosa Anatomy 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DWHJJLTXBKSHJG-HWKANZROSA-N (e)-5-hydroxy-2-methylpent-2-enoic acid Chemical compound OC(=O)C(/C)=C/CCO DWHJJLTXBKSHJG-HWKANZROSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- BEQREZLERZKZQU-UHFFFAOYSA-N tris(dimethylsilyloxy)silane Chemical compound C[SiH](C)O[SiH](O[SiH](C)C)O[SiH](C)C BEQREZLERZKZQU-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なシリコーン修飾アクリル系樹脂特に側鎖
末端に５ｉ−Ｈ基を有する樹脂及びその製法並びに、こ
の樹脂を用いた歯科用接着剤に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel silicone-modified acrylic resin, particularly a resin having a 5i-H group at the end of a side chain, a method for producing the same, and a dental adhesive using this resin. Regarding.
有床義歯患者が義歯を使用する場合に、患者の老化と共
に顎堤の萎縮、顎粘膜の非薄化が生じ、義歯床が顎堤に
安定して適合することが困難となる。また、顎粘膜が咬
合圧に対する緩圧機能を失うため咬合時に疼痛を受ける
という問題がある。これらの諸症状を防ぐために、−般
に義歯床の粘膜面に弾性材料を裏装することが行われて
いる。When a denture patient uses a denture, as the patient ages, the alveolar ridge atrophies and the jaw mucosa becomes thinner, making it difficult for the denture base to stably fit into the alveolar ridge. Another problem is that the jaw mucosa loses its ability to relieve occlusal pressure, resulting in pain during occlusion. In order to prevent these symptoms, the mucosal surface of the denture base is generally lined with an elastic material.
この弾性裏装材としてはシリコーンゴム系のものが優れ
た裏装材として用いられている。特に５０°Ｃ程度迄の
室温で硬化する室温硬化型シリコーンゴム、５０〜１５
０℃程度の低温で硬化する低温硬化型シリコーンゴムが
用いられる。As this elastic lining material, a silicone rubber-based material is used as an excellent lining material. Room-temperature-curing silicone rubber that cures at room temperature, especially up to about 50°C, 50-15
A low-temperature curing silicone rubber that cures at a low temperature of about 0° C. is used.
しかし、シリコーンゴム系裏装材は義歯床のアクリル系
樹脂との接着性に劣る欠点があった。However, silicone rubber lining materials have the disadvantage of poor adhesion to the acrylic resin of the denture base.
そこでこの義歯床と裏装材のシリコーンゴム系材料との
接着剤が種々開発されてきたが、接着性及び耐水性に優
れ、しかも口腔内で長時間使用できる接着剤の研究開発
にその目的が注がれて来きている。最近この接着剤の提
案として、アクリル酸又はメタクリル酸アルキルとアク
リル酸又はメタクリル酸ジメチルビニルシリルアルキル
エステルとの共重合体を用いたシリコーン修飾アクリル
系樹脂が開発された。Therefore, various adhesives have been developed for bonding the denture base and the silicone rubber lining material, but the aim is to research and develop an adhesive that has excellent adhesiveness and water resistance, and can be used for a long time in the oral cavity. It's been pouring in. Recently, as a proposal for this adhesive, a silicone-modified acrylic resin using a copolymer of alkyl acrylic acid or methacrylate and dimethylvinylsilylalkyl acrylic acid or methacrylate has been developed.
前述の従来の技術で得られた義歯床とシリコーンゴム系
裏装材との接着剤もなお、接着性並びに耐水性が充分で
はない。本発明は優れた接着性と耐水性を有する義歯床
とシリコーンゴム系裏装材の接着剤を提供することを目
的とするものである。The adhesive between the denture base and the silicone rubber lining material obtained by the conventional technique described above still does not have sufficient adhesion and water resistance. An object of the present invention is to provide an adhesive for denture bases and silicone rubber lining materials that has excellent adhesive properties and water resistance.
本発明は一般式（１）
（式中、Ｒ３は水素又はメチル基、Ｒ２は低級アルキル
基、Ｒ３は水素又は低級アルキル基、Ｙは低級アルキレ
ン基、ｍ、 ｎは重合数を示す）で表わされる新規シリ
コーン修飾アクリル系樹脂。The present invention is represented by the general formula (1) (wherein R3 is hydrogen or a methyl group, R2 is a lower alkyl group, R3 is hydrogen or a lower alkyl group, Y is a lower alkylene group, and m and n indicate the number of polymerizations). A new silicone-modified acrylic resin.
一般式（ＩＩ）
（ｎ）
ＣＨ２＝Ｃ
Ｃ＝ＯＲ３
０−Ｙ−５ｉ−＋Ｏ３ｉ −Ｈ）３
（式中、Ｒ，、Ｒ１，Ｙは前述と同一意義を有す）で表
わされる化合物と、一般式（ｍ）
（ＩＩＩ）
Ｈ２−Ｃ
０ＯＲ２
（式中、Ｒ１，Ｒ２は前述と同一意義を有す）化合物を
重合開始剤の存在下重合して、一般式（Ｉ）
Ｃ＝ＯＣ＝ＯＲ３
０Ｒ２０−Ｙ−５ｉ＋Ｏ３ｉ −Ｈ）３（式中、Ｒ，、
Ｒ２，Ｒ３，Ｙ、 ｍ、 ｎは前述と同一意義を有す）
新規シリコーン修飾アクリル系樹脂を製造すする方法。A compound represented by the general formula (II) (n) CH2=C C=OR3 0-Y-5i-+O3i -H)3 (wherein R,, R1, and Y have the same meanings as above), General formula (m) (III) H2-C0OR2 (wherein R1 and R2 have the same meanings as above) is polymerized in the presence of a polymerization initiator to form general formula (I) C=OC=OR3 0R20-Y-5i+O3i-H)3 (wherein, R,,
(R2, R3, Y, m, n have the same meanings as above) A method for producing a novel silicone-modified acrylic resin.
並びに前記一般式（１）で表わされる新規シリコーン修
飾アクリル系樹脂を含む、義歯床とシリコーンゴム裏装
材との接着性が優れかつ耐水性の良い歯科用接着剤であ
る。Furthermore, the present invention is a dental adhesive containing a novel silicone-modified acrylic resin represented by the general formula (1), which has excellent adhesiveness between a denture base and a silicone rubber lining material, and has good water resistance.
本発明の一般式（１’ ）で表わされるシリコーン樹脂
は、一般式（ＩＩ）で表わされるアクリロキシ（又はメ
タクリロキシ）アルキレントリス（ジアルキルシロキシ
）シランと一般式（ｍ）で表わされるアクリ酸アルキル
との共重合体である。そして、この樹脂のＲ２はメチル
、エチル、プロピル基等の低級アルキル基であり、メチ
ル基が最適である。Ｒ３は水素又は前記の低級アルキル
基である。また、Ｙはメチレン、エチレン、プロピレン
等の低級アルキレン基であり、プロピレン基が最適であ
る。The silicone resin represented by the general formula (1') of the present invention is a combination of an acryloxy (or methacryloxy) alkylene tris(dialkylsiloxy) silane represented by the general formula (II) and an alkyl acrylate represented by the general formula (m). It is a copolymer. R2 of this resin is a lower alkyl group such as methyl, ethyl, or propyl group, and methyl group is most suitable. R3 is hydrogen or the lower alkyl group described above. Further, Y is a lower alkylene group such as methylene, ethylene, propylene, etc., and a propylene group is most suitable.
一般式（ｎ）で表わされるアクリロキシ（又はメタクリ
ロキシ）アルキレントリス（ジアルキルシロキシ）シラ
ンは、Ｔ、 Ｓ、バラライン（Ｂａｕｒａｉｎ）の方法
（米国特許第３３９８０１７号明細書参照）に準じて合
成した。例えば、水とエーテルの混合溶媒、γ−アクリ
ロキシ（又はメタクリロキシ）アルキレントリメトキシ
シランとジアルキルクロルシランを滴下するだけで得る
ことができる。Acryloxy (or methacryloxy) alkylene tris (dialkylsiloxy) silane represented by general formula (n) was synthesized according to the method of T. S. Baurain (see US Pat. No. 3,398,017). For example, it can be obtained by simply adding dropwise a mixed solvent of water and ether, γ-acryloxy (or methacryloxy) alkylenetrimethoxysilane, and dialkylchlorosilane.
この反応は、γ−アクリロキシ（又はメタクリロキシ）
アルキレントリメトキシシランが加水分解され、この化
合物中のメトキシ基が水酸基で置換され、次にジアルキ
ルクロルシランと反応する結果、−分子中に１〜３個の
５ｉ−Ｈ基（シリリジン基）が導入される。This reaction involves γ-acryloxy (or methacryloxy)
The alkylenetrimethoxysilane is hydrolyzed, the methoxy group in this compound is replaced with a hydroxyl group, and then it reacts with the dialkylchlorosilane, resulting in the introduction of 1 to 3 5i-H groups (silyridine groups) into the molecule. be done.
以上のようにして得られた一般式（ｎ）で表わされるア
クリロキシ（又はメタクリロキシ）アルキレントリス（
ジアルキルシロキシ）シランは、次に一般式（ｍ）で表
わされるアクリル酸又はメタクリル酸アルキルエステル
と共重合して、本発明の化合物（Ｉ）を得ることができ
る。Acryloxy (or methacryloxy) alkylene tris represented by general formula (n) obtained as above (
The dialkylsiloxy)silane can then be copolymerized with an acrylic acid or methacrylic acid alkyl ester represented by the general formula (m) to obtain the compound (I) of the present invention.
この共重合は、一般の共重合体を得る方法と同様に、上
記アクリロキシ（又はメタクリロキシ）アルキレントリ
ス（ジアルキルシロキシ）シラン〔式（■）〕とアクリ
ル酸アルキル又はメタクリル酸アルキル〔式（■）〕を
ＡＩＢＮ。This copolymerization is carried out using the above acryloxy (or methacryloxy) alkylene tris (dialkylsiloxy) silane [formula (■)] and alkyl acrylate or alkyl methacrylate [formula (■)] in the same way as the method for obtaining general copolymers. AIBN.
ＢＰＯ，過酸化アセチル等の重合開始剤の存在下イソプ
ロパツール、トルエン、キシレン等の溶解を用い不活性
ガス下で６０℃前後に加熱して行う。This is carried out by dissolving isopropanol, toluene, xylene, etc. in the presence of a polymerization initiator such as BPO, acetyl peroxide, etc. and heating to around 60° C. under an inert gas.
式（ｎ）の化合物（Ｉｎ）の化合物のモル比を適宜調整
し式（１）の重合物の性状を変化し得るが、通常、式（
ｎ）の化合物対式（ＩＩＩ）の化合物の反応モル比（１
：１２）とする。The properties of the polymer of formula (1) can be changed by appropriately adjusting the molar ratio of the compound (In) of formula (n);
n) to the compound of formula (III) (1
:12).
以上のようにして得られた本発明の新規シリコーン修飾
アクリル系樹脂〔式（Ｉ）〕を歯科用接着剤とするには
、この樹脂を有機溶媒、好適にはトルエンの適宜の濃度
、好適には１０ｗｔ％前後に溶解して接着剤とする。In order to use the novel silicone-modified acrylic resin [formula (I)] of the present invention obtained as described above as a dental adhesive, this resin is treated with an organic solvent, preferably toluene, at an appropriate concentration. is dissolved to about 10 wt% and used as an adhesive.
本発明の式（Ｉ）で表わされるシリコーン修飾アクリル
系樹脂は、その側鎖の末端にシリリジン基を有するため
加水分解されにくく、かつ耐水性が高い作用効果を有す
るものである。そしてシリリジン基は裏装材のシリコー
ンゴム中のＳｉ−ビニル基と反応し強固に一接着し歯科
用接着剤としての作用も優れている。The silicone-modified acrylic resin represented by formula (I) of the present invention has a silylysine group at the end of its side chain, so it is resistant to hydrolysis and has high water resistance. The silyridine group reacts with the Si-vinyl group in the silicone rubber of the backing material to form a strong bond and has excellent functionality as a dental adhesive.
次に本発明の実施例並ひに本発明のシリコーン系樹脂の
効果試験を述べる。Next, examples of the present invention and effectiveness tests of the silicone resin of the present invention will be described.
例１．γ−メタクロリロキシプロピルトリス（ジメチル
シロキシ）シランの合成
水４１．０ｄとエーテル４０．０−を混合した溶液中に
、γ−メタクリロキシプロピルトリメトキシシラン２０
．０ ｇとジメチルクロルシラン４５．４ ｇの混合溶
液を滴下しながら２時間撹拌し反応させた。発熱するの
で氷冷し、その後常温で一日放置した。分液漏斗で水相
を除き、エーテル相を４回水洗し、その後無水硫酸ナト
リウムで乾燥した。エーテル留去後、ハイドロキノンを
加え減圧蒸留により精製し、γ−メタクロリロキシプロ
ピルトリス（ジメチルシロキシ）シランを得た。Example 1. Synthesis of γ-methacryloxypropyltris(dimethylsiloxy)silane In a solution of 41.0 d of water and 40.0 d of ether, 20 d of γ-methacryloxypropyltrimethoxysilane was added.
．． A mixed solution of 0 g of dimethylchlorosilane and 45.4 g of dimethylchlorosilane was added dropwise and stirred for 2 hours to react. Since it generated heat, it was cooled on ice and then left at room temperature for one day. The aqueous phase was removed using a separatory funnel, and the ether phase was washed four times with water and then dried over anhydrous sodium sulfate. After distilling off the ether, hydroquinone was added and the mixture was purified by vacuum distillation to obtain γ-methacrylolyloxypropyltris(dimethylsiloxy)silane.
例２．γ−メタクロリロキシブロピルトリス（ジメチル
シロキシ）シランとメタクリル酸共重合体〔式（Ｉ）〕
の合成
重合用ガラス封管中にｙ−メタクロリロキシプロピルト
リス（ジメチルシロキシ）シラン２．８ｇ、 メタク
リル酸９．３ｇ、 トルエン５０ｎ＋Ｑ及び重合開始
剤（ＡＩＢＮ） ０．０６ｇを入れ、窒素置換し、後に
封管して６０°Ｃで５０時間反応させγ−メタクロリロ
キシプロピルトリス（ジメチルシロキシ）シランとメタ
クリル酸共重合体を得る。Example 2. γ-methacryloxypropyltris(dimethylsiloxy)silane and methacrylic acid copolymer [Formula (I)]
2.8 g of y-methacryloxypropyltris(dimethylsiloxy)silane, 9.3 g of methacrylic acid, 50n+Q toluene, and 0.06 g of a polymerization initiator (AIBN) were placed in a glass sealed tube for synthesis polymerization, and the tube was replaced with nitrogen. Afterwards, the tube is sealed and reacted at 60°C for 50 hours to obtain a copolymer of γ-methacryloxypropyltris(dimethylsiloxy)silane and methacrylic acid.
本物質の赤外線吸収スペクトル並びに核磁気共鳴スペク
トル（’Ｈ−ＮＭＲ（６０ＭＨ２，ＣＤ（Ｊ１３） 〕
を第１図、第２図で示す。’Ｈ−ＮＭＲスペクトルで明
らかなようにｌ、 Ｏｐｐｍ付近にメタクリル基中のプ
ロトンが、２．Ｏｐｐｍ付近に主鎖中のメチレンのプロ
トンが３．５ｐｐｍ付近にはメタクリル酸中のメトキシ
基のプロトンが認められる。また、Ｏ，ｌｐｐｍ付近に
はγ−メタクロリロキシプロピルトリス（ジメチルシロ
キシ）シラン中のシラン上のジメチルシロキシ中メチル
のプロトンが、４．７ｐｐｍ付近にはシリリシン基のプ
ロトンピークが認められる。Infrared absorption spectrum and nuclear magnetic resonance spectrum ('H-NMR (60MH2, CD (J13)) of this substance
are shown in Figures 1 and 2. As is clear from the 'H-NMR spectrum, there are protons in the methacrylic group near 1 and Oppm, and 2. A proton of methylene in the main chain is observed near Oppm, and a proton of a methoxy group in methacrylic acid is observed near 3.5 ppm. Further, a proton peak of methyl in dimethylsiloxy on the silane in γ-methacryloxypropyltris(dimethylsiloxy)silane is observed near O, lppm, and a proton peak of a silylysine group is observed near 4.7 ppm.
例３．歯歯科接接剤
例２で合成したγ〜メタクロリロキシプロピルトリス（
ジメチルシロキシ）シランとメタアクリル酸共重合体を
トルエンで１０ｗｔ％濃度の溶液として接着剤とした。Example 3. γ ~ methachloryloxypropyl tris (
Dimethylsiloxy) silane and methacrylic acid copolymer were dissolved in toluene at a concentration of 10 wt % to prepare an adhesive.
本発明のγ−メタクロリロキシプロピルトリス（ジメチ
ルシロキシ）シランとメタアクリル酸共重合体の接着試
験は次の通りである。The adhesion test of the γ-methacryloxypropyltris(dimethylsiloxy)silane and methacrylic acid copolymer of the present invention was as follows.
接着試験
１）供試試料
ａ） 実施例２により得られた本発明のγメタクロすロ
キシプロビルトリス（ジメチルシロキシ）シランの１０
ｗｔ％トルエン溶液。Adhesion test 1) Test sample a) 10 of the γ metachlorosuloxyprobiltris(dimethylsiloxy)silane of the present invention obtained in Example 2
wt% toluene solution.
ｂ） ヒドロキシエチルメタクリル酸とメチルメタクリ
ル酸の共重合体２．４７ｇとトリエチルアミン０．２４
ｇをテトラヒドロフラン５０ｍΩに溶かした溶液に、ジ
メチルビニルクロライド０．２９ｇをテトラヒドロフラ
ン２５ ｍＱに溶かした溶液を滴下し、１時間撹拌しな
がら反応させ、発熱するので冷却する。b) 2.47 g of copolymer of hydroxyethyl methacrylic acid and methyl methacrylic acid and 0.24 g of triethylamine
A solution of 0.29 g of dimethylvinyl chloride dissolved in 25 mQ of tetrahydrofuran is added dropwise to a solution of 0.29 g of dimethylvinyl chloride dissolved in 50 mQ of tetrahydrofuran, and the mixture is reacted with stirring for 1 hour. Cooling is performed to avoid heat generation.
得られたトリエチルアミンの塩酸塩を 決別し、テトラヒドロフランを留去し。The obtained triethylamine hydrochloride Separate and distill off the tetrahydrofuran.
後メタノールを非溶媒としてメタクリル酸メチルとメタ
クリル酸ジメチルとニルシリルエチルエステルとの共重
合体を得る。Then, a copolymer of methyl methacrylate, dimethyl methacrylate, and nylsilylethyl ester is obtained using methanol as a nonsolvent.
この共重合体のｌ０ｗｔ％トルエン溶液。A 10 wt% toluene solution of this copolymer.
２）試験材料
接着試験に際して、義歯床に相当するものとしてアクリ
ル樹脂棒（ポリメタクリル酸メチル）を用い、また付加
型シリコーンゴム裏装材としてＦＡ／ＦＢゴム（ジメチ
ルポリシロキサン） 、 ＥＡ／２Ｂゴム（ジメチルポ
リシロキサン） 、２Ａ７２Ｂゴム（ジメチルポリシロ
キサン）を用いた。2) Test materials During the adhesion test, an acrylic resin rod (polymethyl methacrylate) was used as a denture base, and FA/FB rubber (dimethylpolysiloxane) and EA/2B rubber were used as additional silicone rubber lining materials. (dimethylpolysiloxane) and 2A72B rubber (dimethylpolysiloxane) were used.
３）試験方法
直径８ｍｍのアクリル樹脂棒を、長さ３ ｃｍに切断し
、切断面を旋盤で平らに仕上げた。供試接着剤を用いて
試験材料の付加型シリコーンゴム１ｍｍ厚さのものを接
着して試験体とした。試験体はＦＡ／ＦＢゴムを本発明
の接着剤を用いてアクリル樹脂棒に接着したもの、ＥＡ
／２Ｂゴムを本発明の接着剤を用いてアクリル樹脂棒に
接着したもの、２Ａ／２Ｂゴムを本発明の接着剤を用い
てアクリル樹脂棒に接着したもの及び対照としてＦＡ／
ＦＢゴムを対照接着剤（ｂ）を用いてアクリル樹脂棒に
接着したものを各５本ずつ作り、それぞれ８０℃の水温
中に浸漬し、１７日間の日毎の接着強さを引張り試験に
より測定した。この測定は、インストロン型万能試験機
（シンコー社製、ＴＣＭ ５００ ＣＲ）を用い、引張
り速度３０Ｍ／分で測定した。3) Test method An acrylic resin rod with a diameter of 8 mm was cut into a length of 3 cm, and the cut surface was finished flat with a lathe. A test piece was prepared by adhering a 1 mm thick piece of additive-type silicone rubber as a test material using the test adhesive. The test specimen was FA/FB rubber adhered to an acrylic resin rod using the adhesive of the present invention, and EA
/2B rubber adhered to an acrylic resin rod using the adhesive of the present invention, 2A/2B rubber adhered to an acrylic resin rod using the adhesive of the present invention, and FA/2B rubber as a control.
Five sticks of FB rubber were bonded to acrylic resin rods using the control adhesive (b), each of which was immersed in water at a temperature of 80°C, and the adhesion strength was measured daily for 17 days by a tensile test. . This measurement was performed using an Instron type universal testing machine (manufactured by Shinko Co., Ltd., TCM 500 CR) at a tensile speed of 30 M/min.
４）試験結果 本試験の結果を第３図で示す。4) Test results The results of this test are shown in Figure 3.
この結果より明らかな通り、本発明の接着剤は対照に比
しアクリル樹脂とシリコーンコムに対し極めて強固な接
着力を有する。As is clear from the results, the adhesive of the present invention has extremely strong adhesion to acrylic resin and silicone comb compared to the control.
本発明は以上延べた通り、義歯素材であるアクリル樹脂
と義歯床の裏装材であるシリコーンゴムとの接着が極め
て強く、しがも耐水性に優れ、口腔内で長時間使用する
ことができる新規なシリコーン修飾アクリル系樹脂歯科
用接着剤として極めて有用な発明である。As described above, the present invention has extremely strong adhesion between the acrylic resin that is the denture material and the silicone rubber that is the lining material of the denture base, has excellent water resistance, and can be used in the oral cavity for a long time. This invention is extremely useful as a new silicone-modified acrylic resin dental adhesive.
第１図は本発明の接着剤の主成分の代表的物質のｙ−メ
タクロリロキシブロピルトリス（ジメチルシロキシ）シ
ランとメタクリル酸共重合体の赤外線吸収スペクトルを
示す。
第２図は同物質の核磁気共鳴スペクトルを示す。
第３図は本発明の歯科用接着剤の接着力を対照と対比し
て示した図面である。FIG. 1 shows the infrared absorption spectrum of y-methacryloxypropyltris(dimethylsiloxy)silane and methacrylic acid copolymer, which are representative substances as the main components of the adhesive of the present invention. Figure 2 shows the nuclear magnetic resonance spectrum of the same material. FIG. 3 is a drawing showing the adhesive strength of the dental adhesive of the present invention in comparison with a control.
Claims (1)
キル基、Ｒ＿３は水素又は低級アルキル基、Ｙは低級ア
ルキレン基、ｍ、ｎは重合数を示す）で表わされる新規
シリコーン修飾アクリル 系樹脂。 ２、式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿１は水素又はメチル基、Ｒ＿３は水素又は
低級アルキル基、Ｙは低級アルキレン基を示す）、 で表わされる化合物に重合開始剤の存在下 式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒ＿１は先と同一意義を有し、Ｒ＿２は低級ア
ルキル基を示す） で表わされる化合物を共重合させることを 特徴とする。 式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｙは先と同一意義を
有し、ｍ、ｎは重合数を示す） で表わされる新規シリコーン修飾アクリル 系樹脂の製造方法。 ３、式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｒ＿１は水素又はメチル基、Ｒ＿２は低級アル
キル基、Ｒ＿３は水素又は低級アルキル基、Ｙは低級ア
ルキレン基、ｍ、ｎは重合数を示す）で表わされる新規
シリコーン修飾アクリル 系樹脂を含む歯科用接着剤。[Claims] 1. Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is hydrogen or a methyl group, R_2 is a lower alkyl group, R_3 is hydrogen or a lower alkyl group, A novel silicone-modified acrylic resin represented by Y is a lower alkylene group and m and n indicate the number of polymerizations. 2. Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1 is hydrogen or a methyl group, R_3 is hydrogen or a lower alkyl group, and Y is a lower alkylene group), Represented by In the presence of a polymerization initiator, the compound is represented by the formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1 has the same meaning as above, and R_2 represents a lower alkyl group) It is characterized by copolymerizing compounds. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1, R_2, R_3, and Y have the same meanings as above, and m and n indicate the number of polymerizations.) A method for producing silicone-modified acrylic resin. 3. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is hydrogen or a methyl group, R_2 is a lower alkyl group, R_3 is hydrogen or a lower alkyl group, Y is a lower alkylene group, A dental adhesive containing a novel silicone-modified acrylic resin represented by m and n indicating the number of polymerizations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180931A JPH0611683B2 (en) | 1990-07-09 | 1990-07-09 | Dental adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2180931A JPH0611683B2 (en) | 1990-07-09 | 1990-07-09 | Dental adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0468007A true JPH0468007A (en) | 1992-03-03 |
| JPH0611683B2 JPH0611683B2 (en) | 1994-02-16 |
Family
ID=16091783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2180931A Expired - Fee Related JPH0611683B2 (en) | 1990-07-09 | 1990-07-09 | Dental adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611683B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007107A1 (en) * | 1993-09-10 | 1995-03-16 | Smith & Nephew Plc | Surgical cements |
| EP0826359A3 (en) * | 1996-09-03 | 2000-04-19 | VOCO GmbH | Adhesive as a coupling agent between elastic and rigid materials |
| JP2002053418A (en) * | 2000-08-10 | 2002-02-19 | Gc Corp | Adhesive composition for dental silicone rubber |
| US6566479B1 (en) * | 1998-01-22 | 2003-05-20 | Kettenbach Gmbh & Co. Kg | Relining for prostheses and process the manufacturing thereof |
| US6866742B2 (en) | 2001-08-07 | 2005-03-15 | Tokuyama Corporation | Adhesive for silicone rubber lining materials |
| JP2012532960A (en) * | 2009-07-07 | 2012-12-20 | コンバテック テクノロジーズ インコーポレイテッド | Amphiphilic silicone copolymers for the application of pressure sensitive adhesives |
| JP2019151595A (en) * | 2018-03-05 | 2019-09-12 | 株式会社トクヤマデンタル | Dental composition |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2168935A1 (en) | 2008-09-29 | 2010-03-31 | Siemens Aktiengesellschaft | Material compound for producing a fire-retardant material and its application and fire-retardant moulding body and method for its manufacture |
| EP2218873A1 (en) | 2009-02-17 | 2010-08-18 | Siemens Aktiengesellschaft | Rotor section for a rotor of a turbo machine, rotor blade for a turbo machine and blocking element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63216044A (en) * | 1987-03-05 | 1988-09-08 | Nippon Zeon Co Ltd | Pattern forming material |
| JPH01284513A (en) * | 1988-05-11 | 1989-11-15 | Chuo Rika Kogyo Kk | Acrylic emulsion composition |
-
1990
- 1990-07-09 JP JP2180931A patent/JPH0611683B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63216044A (en) * | 1987-03-05 | 1988-09-08 | Nippon Zeon Co Ltd | Pattern forming material |
| JPH01284513A (en) * | 1988-05-11 | 1989-11-15 | Chuo Rika Kogyo Kk | Acrylic emulsion composition |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995007107A1 (en) * | 1993-09-10 | 1995-03-16 | Smith & Nephew Plc | Surgical cements |
| EP0826359A3 (en) * | 1996-09-03 | 2000-04-19 | VOCO GmbH | Adhesive as a coupling agent between elastic and rigid materials |
| US6566479B1 (en) * | 1998-01-22 | 2003-05-20 | Kettenbach Gmbh & Co. Kg | Relining for prostheses and process the manufacturing thereof |
| US6911514B2 (en) * | 1998-01-22 | 2005-06-28 | Kettenbach Gmbh & Co. Kg | Relining for prostheses and process for the manufacturing thereof |
| JP2002053418A (en) * | 2000-08-10 | 2002-02-19 | Gc Corp | Adhesive composition for dental silicone rubber |
| JP4703825B2 (en) * | 2000-08-10 | 2011-06-15 | 株式会社ジーシー | Adhesive composition for dental silicone rubber |
| US6866742B2 (en) | 2001-08-07 | 2005-03-15 | Tokuyama Corporation | Adhesive for silicone rubber lining materials |
| JP2012532960A (en) * | 2009-07-07 | 2012-12-20 | コンバテック テクノロジーズ インコーポレイテッド | Amphiphilic silicone copolymers for the application of pressure sensitive adhesives |
| JP2012532959A (en) * | 2009-07-07 | 2012-12-20 | コンバテック テクノロジーズ インコーポレイテッド | Pressure sensitive silicone adhesive with amphiphilic copolymer |
| JP2019151595A (en) * | 2018-03-05 | 2019-09-12 | 株式会社トクヤマデンタル | Dental composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611683B2 (en) | 1994-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5237082A (en) | Radiation-curable silicone elastomers and pressure sensitive adhesives | |
| FI71482B (en) | FLOATING EQUIPMENT FOR THE PURPOSE OF THE SPRICKOR I TRENDING THE FOUNDATION FOR THE FRAME STATION | |
| CN103370041B (en) | Comprise the dental composition of the unsaturated addition-clastogen of ethylenic | |
| US5476912A (en) | Silicone-modified acrylic copolymer and adhesive thereof | |
| EP0421643B1 (en) | Radiation-curable silicone elastomers and pressure sensitive adhesives | |
| JPS61293960A (en) | (meth)acrylic acid esters | |
| JP2011515513A (en) | Low shrinkage multifunctional SSQ resin | |
| KR101164302B1 (en) | Phosphate ester compound, metal salt thereof, dental material, and dental composition | |
| JPH0468007A (en) | New silicone-modified acrylic resin, its production and dental adhesive prepared by using said resin | |
| JPS5930877A (en) | Adhesive | |
| JPH08104664A (en) | New(meta)acrylate monomer and denture base composition containing the same | |
| US3540126A (en) | Fluoroalkoxyalkyl 2 - cyanoacrylate compositions used in tooth treatment | |
| US4816597A (en) | Dental restorative materials based upon blocked isocyanates | |
| JP2865794B2 (en) | Adhesive composition | |
| JPH02212455A (en) | Itaconic acid monoester compound and adhesive containing same compound | |
| JP2742268B2 (en) | Dental adhesive made of silicone resin | |
| DE50211862D1 (en) | POLYSILOXANO SOLE, PROCESS FOR THEIR PREPARATION AND ITS USE | |
| JPH0770246A (en) | Silicone-modified acrylic random copolymer and adhesive | |
| WO2005090281A1 (en) | (meth)acrylic compound and use thereof | |
| JP3937576B2 (en) | Ophthalmic lens polymer and method for modifying the same | |
| KR100341142B1 (en) | Methacrylate, preparing method thereof and dental resin composition containing the same | |
| EP0211408A2 (en) | Dental materials | |
| JPH0753935A (en) | Adhesive | |
| JP2783581B2 (en) | Phosphazene derivative and radiopaque material containing the same | |
| JPH01238553A (en) | Diacrylate or dimethacrylate having fluorine-containing bisphenol group as skeleton and polymeric material composed of said compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |