JPH01238553A - Diacrylate or dimethacrylate having fluorine-containing bisphenol group as skeleton and polymeric material composed of said compound - Google Patents
Diacrylate or dimethacrylate having fluorine-containing bisphenol group as skeleton and polymeric material composed of said compoundInfo
- Publication number
- JPH01238553A JPH01238553A JP6028888A JP6028888A JPH01238553A JP H01238553 A JPH01238553 A JP H01238553A JP 6028888 A JP6028888 A JP 6028888A JP 6028888 A JP6028888 A JP 6028888A JP H01238553 A JPH01238553 A JP H01238553A
- Authority
- JP
- Japan
- Prior art keywords
- dimethacrylate
- fluorine
- diacrylate
- skeleton
- bis
- 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052731 fluorine Inorganic materials 0.000 title claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 17
- 239000011737 fluorine Substances 0.000 title claims description 17
- 125000004386 diacrylate group Chemical group 0.000 title claims description 16
- 150000001875 compounds Chemical class 0.000 title abstract description 13
- 239000000463 material Substances 0.000 title abstract description 9
- 239000000126 substance Substances 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000004851 dental resin Substances 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- XAFJMCUBVZTMDB-UHFFFAOYSA-N 2-[4-[1,1,1,3,3,3-hexafluoro-2-[4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OCCO)C=C1 XAFJMCUBVZTMDB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 14
- 239000000178 monomer Substances 0.000 description 8
- -1 acryloxy group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000005548 dental material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 4
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229920001002 functional polymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- VIYWVRIBDZTTMH-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 VIYWVRIBDZTTMH-UHFFFAOYSA-N 0.000 description 2
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- LKJWDWUXGCKFPN-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 LKJWDWUXGCKFPN-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SZTUJDINRYGMRV-UHFFFAOYSA-N [4-[1,1,1,3,3,3-hexafluoro-2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC(=O)C=C)C=C1 SZTUJDINRYGMRV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は新規な含フッ素ビスフェノール基を骨格とする
ジアクリレートまたはジメタクリレートおよびこれらを
成分とする高分子材料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel diacrylate or dimethacrylate having a fluorine-containing bisphenol group as a backbone, and a polymeric material containing these as a component.
本発明により提供される新規な含フッ素ビスフェノール
基を骨格とするジアクリレートまたはジメタクリレート
・はそれ自体で重合させるか、または各種のオレフィン
性二重結合を有する化合物と共重合させることによって
、種々の有用な含フッ素ポリマーとなり、熱的・化学的
安定性、抗水性、潤滑性に優れた高分子材料として種々
の応用分野への適用が可能であり、例えば、低屈折率お
よび常温硬化性の要求される光通信ケーブル用光学接着
剤や低屈折率、耐水性および常温硬化性の要求される歯
科用樹脂などとして利用することができる０本発明が特
に有用に用いられるのは、口腔内の湿潤環境下で耐久性
が要求される歯科用樹脂である。The novel diacrylate or dimethacrylate having a skeleton of a fluorine-containing bisphenol group provided by the present invention can be polymerized by itself or copolymerized with a compound having various olefinic double bonds to form various types of diacrylate or dimethacrylate. It is a useful fluorine-containing polymer and can be applied to various application fields as a polymer material with excellent thermal and chemical stability, water resistance, and lubricity. It can be used as an optical adhesive for optical communication cables, and as a dental resin that requires low refractive index, water resistance, and room temperature hardening.The present invention is particularly useful for moistening the oral cavity. This is a dental resin that requires durability under environmental conditions.
［従来の技術］
従来、ジアクリレートまたはジメタクリレートは、光学
材料、歯科材料、各種高分子の架橋剤等、機能性高分子
として広い応用分野で用いられているが、近年、ますま
す高い機能、例えば、より高い耐熱性、化学的安定性、
潤滑性、抗水性、低屈折率等が要求されるようになって
きている。[Prior Art] Diacrylate or dimethacrylate has been used in a wide range of application fields as functional polymers, such as optical materials, dental materials, and crosslinking agents for various polymers. For example, higher heat resistance, chemical stability,
Lubricity, water resistance, low refractive index, etc. are increasingly required.
しかしながら、これらの要求に対し、通常のフッ素を含
有していないビスフェノール基を骨格とするジアクリレ
ートまたはジメタクリレートあるいは脂肪族系ジアクリ
レートまたはジメタクリレートでは必ずしも満足のいく
ものではないのが実情である。However, the reality is that these requirements are not necessarily satisfied with ordinary diacrylates or dimethacrylates having a skeleton of bisphenol groups that do not contain fluorine, or aliphatic diacrylates or dimethacrylates.
例えば、歯科用樹脂としては、従来メチルメタクリレー
ト系レジンやポリエチレングリコールジメタクリレート
系レジンあるいはフッ素を含有していないビスフェノー
ル基を骨格とするジメタクリレート、例えば、２，２−
ビス［４−（２’−ヒドロキシ−３゛−メタクリロキシ
プロポキシ）フェニル］プロパン（米国特許第３１７９
６２３号、以下Ｂｉｓ−ＧＭＡと略記する）や２．２−
ビス（４−メタクリロキシポリエトキシフェニル〉プロ
パン（米国特許第３５９７３８９号、以下Ｂ１５−ＭＰ
ＥＰＰと略記する）などが知られているが、口腔内とい
う湿潤環境下では十分な耐久性を有さないという欠点が
あった。さらに、歯の修復材料である歯冠用レジンや充
填用レジンでは、歯質に近い強度が要求されるため、無
機質のガラスフィラーを混入したコンポジットレジンが
採用されており、近年これらレジンの硬化法として光重
合法が確立され、その主流となっている。この際均質な
硬化物を得るためにはガラスフィラーとマトリックスレ
ジンとの屈折率の整合性が必要であり、レジンの低屈折
率化が要求されている。For example, as dental resins, conventional methyl methacrylate resins, polyethylene glycol dimethacrylate resins, or dimethacrylates with a skeleton of bisphenol groups that do not contain fluorine, such as 2,2-
Bis[4-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (U.S. Pat. No. 3179)
No. 623, hereinafter abbreviated as Bis-GMA) and 2.2-
Bis(4-methacryloxypolyethoxyphenyl)propane (US Pat. No. 3,597,389, hereinafter B15-MP
EPP (abbreviated as EPP) is known, but it has the drawback that it does not have sufficient durability in the humid environment of the oral cavity. Furthermore, resins for crowns and fillings, which are tooth restoration materials, are required to have strength close to that of tooth structure, so composite resins containing inorganic glass fillers have been adopted, and in recent years, methods for curing these resins have been developed. The photopolymerization method has been established as a method and has become the mainstream. At this time, in order to obtain a homogeneous cured product, it is necessary to match the refractive index of the glass filler and the matrix resin, and a lower refractive index of the resin is required.
このため、ビスフェノール基を骨格とするジアクリレー
ト（例えばＢｉｓ−ＧＭＡやＢｉｓ−ＭＰＥＰＰ）に比
較して屈折率が低い脂肪族系ジメタクリレート（例えば
、ポリエチレングリコールジメタクリレート）を多量に
配合させる方法が用いられている。しかし、脂肪族系ジ
メタクリレートはビスフェノール基を骨格とするジメタ
クリレートに比較して吸水しやすく、また強度も低いと
いう欠点があった。For this reason, a method is used in which a large amount of aliphatic dimethacrylate (for example, polyethylene glycol dimethacrylate) is blended, which has a lower refractive index than diacrylate having a bisphenol group skeleton (for example, Bis-GMA or Bis-MPEPP). It is being However, aliphatic dimethacrylates have disadvantages in that they absorb water more easily and have lower strength than dimethacrylates having a bisphenol group as a backbone.
一方、ビスフェノール基を骨格とするジメタクリレート
は、強度、耐水性に優れるものの、屈折率が高く、ガラ
スフィラーとの屈折率差が大きいため、このものを多量
に含有させたコンポジットレジンは光透過性が悪く、そ
の硬化体は不均質な重合体となってしまうなどの問題点
がある。このように、従来のジメタクリレートでは低屈
折率を有し、かつ強度、耐久性に優れていることが要求
される歯科材料の用途においては、この二つの所要性質
を同一化合物で満足することができるものが要望されて
いるにもかかわらず、いまだ見いだされていないのが実
情である。On the other hand, although dimethacrylate, which has a bisphenol group as its backbone, has excellent strength and water resistance, it has a high refractive index and a large difference in refractive index with glass filler, so composite resin containing a large amount of this dimethacrylate has low light transmittance. There are problems in that the cured product becomes a non-uniform polymer. In this way, for dental material applications where conventional dimethacrylates are required to have a low refractive index and be superior in strength and durability, it is possible to satisfy these two required properties with the same compound. Despite the demand for something that can be done, the reality is that it has not yet been found.
［発明が解決しようとする問題点コ
本発明の目的の一つは光学材料、歯科材料、各種高分子
架橋剤等の機能性高分子材料として有用な耐熱性、化学
的安定性、潤滑性、抗水性、強度等に優れており、合わ
せて低屈折率化をはかることのできる材料の提供である
。また、特に歯科材料に限定すれば、低屈折率を有し、
かつ強度、耐水性に優れた機能性高分子の開発にある。[Problems to be Solved by the Invention] One of the objects of the present invention is to provide heat resistance, chemical stability, lubricity, and the like useful as functional polymer materials such as optical materials, dental materials, and various polymer crosslinking agents. The purpose of the present invention is to provide a material that has excellent water resistance, strength, etc., and can also have a low refractive index. In addition, if it is limited to dental materials in particular, it has a low refractive index,
The goal is to develop functional polymers that have excellent strength and water resistance.
［問題点を解決するための手段］
本発明者らは、かかる点に注力し、鋭意検討の結果、含
フッ素置換基を有する化合物は蒸化合物と比較して屈折
率が低下する事実に着目し、ビスフェノール基を骨格と
するジアクリレートあるいはジメタクリレートの一部を
フッ素置換することにより所期の目、的を達成できるこ
とを見いだし本発明に到達した。[Means for Solving the Problems] The present inventors focused on this point, and as a result of intensive studies, they focused on the fact that compounds having fluorine-containing substituents have a lower refractive index than vaporized compounds. The present invention has been achieved by discovering that the desired object can be achieved by substituting a part of diacrylate or dimethacrylate with bisphenol group backbone with fluorine.
すなわち本発明は一般式
（式中、Ｒは水素原子またはメチル基を表わす、）で示
される含フッ素ビスフェノール基を骨格とするジアクリ
レートまたはジメタクリレートおよび一般式（１）で示
される含フッ素ビスフェノール基を骨格とするジアクリ
レートまたはジメタクリレートを成分とする高分子材料
である。That is, the present invention relates to a diacrylate or dimethacrylate having a skeleton of a fluorine-containing bisphenol group represented by the general formula (wherein R represents a hydrogen atom or a methyl group) and a fluorine-containing bisphenol group represented by the general formula (1). It is a polymeric material whose component is diacrylate or dimethacrylate with a skeleton of
従来、含フッ素ビスフェノール基を骨格とするジアクリ
レートまたはジメタクリレートについて報告された例が
皆無というわけではなく、特開昭６１−２３８７６１号
には含フッ素ビスフェノール基に直接アクリロキシ基ま
たはメタクリロキシ基を導入した２、２−ビス（４−ア
クリロキシフェニル）へキサフルオロプロパン、２．２
−ビス（４−メタクリロキシフェニル）へキサフルオロ
プロパンについて開示されている。しかし、これらは、
いずれも結晶性モノマーであり、他のモノマーとの相溶
性に乏しく、その使用範囲が限定されるという欠点を有
している。また、含フッ素ビスフェノール基を骨格とす
るジェポキシ化合物とアクリル酸の付加物として２，２
−ビス［４−（２’−ヒドロキシ−３°−アクリロキシ
プロポキシ）フェニル］へキサフルオロプロパン（特開
昭６２−２２１６５４号）が知られているが、このもの
は分子内に水酸基を有しているため、耐水性に劣るとい
う欠点がある。Until now, there have been no reports of diacrylates or dimethacrylates having a fluorine-containing bisphenol group as a backbone, and JP-A No. 61-238761 describes a method in which an acryloxy group or a methacryloxy group was directly introduced into a fluorine-containing bisphenol group. 2,2-bis(4-acryloxyphenyl)hexafluoropropane, 2.2
-bis(4-methacryloxyphenyl)hexafluoropropane. However, these
All of them are crystalline monomers and have the disadvantage of poor compatibility with other monomers, which limits their range of use. In addition, 2,2
-Bis[4-(2'-hydroxy-3°-acryloxypropoxy)phenyl]hexafluoropropane (JP-A-62-221654) is known, but this product has a hydroxyl group in the molecule. Because of this, it has the disadvantage of poor water resistance.
本発明の化合物はこれら従来公知の化合物の欠点を一掃
するものであり、具体的にはＰ−）−ルエンスルフオン
酸を触媒として対応するジオールとアクリル酸あるいは
メタクリル酸との脱水反応により合成できる。The compounds of the present invention eliminate the drawbacks of these conventionally known compounds, and can be specifically synthesized by a dehydration reaction between the corresponding diol and acrylic acid or methacrylic acid using P-)-luenesulfonic acid as a catalyst.
本発明のジアクリレートまたはジメタクリレートはフッ
素原子を含有することにより、フッ素を含有しないビス
フェノール基を骨格とするジアクリレートまたはジメタ
クリレートに比較して低屈折率を有する。従って、例え
ばこれらを歯科材料用のコンポジットレジンのマトリッ
クスレジンとして用いる場合、ガラスフィラーとの屈折
率整合性が改善され、より均質な硬化体が得られる。ま
た、本発明化合物は嵩高な含フッ素ビスフェノール骨格
を有しており、ガラスフィラーを用いなくても機械的強
度、耐久性、耐汚染性等に極めて優れており、単独での
使用も十分可能である。Since the diacrylate or dimethacrylate of the present invention contains a fluorine atom, it has a lower refractive index than a diacrylate or dimethacrylate whose skeleton is a bisphenol group that does not contain fluorine. Therefore, for example, when these are used as a matrix resin for a composite resin for dental materials, the refractive index matching with the glass filler is improved and a more homogeneous cured body can be obtained. In addition, the compound of the present invention has a bulky fluorine-containing bisphenol skeleton, and has excellent mechanical strength, durability, stain resistance, etc. even without the use of glass fillers, and can be used alone. be.
本発明化合物は前記したような硬化体としての物性のほ
か、室温で液状モノマーであるという優れた特徴を有し
ており、他のモノマーとの相溶性に優れ、他のオレフィ
ン性二重結合を持っモノマーとの共重合も常温硬化で行
うことができ、分子内に重合性基としてアクリロキシ基
またはメタクリロキシ基を有するため、はとんどの重合
様式で硬化することができる０例えば、過酸化物を加え
加熱重合、過酸化物−芳香族第３級アミンのレドックス
系重合開始剤を用いれば常温重合も可能であり、さらに
光重合開始剤あるいは増感剤としてベンゾインエチルエ
ーテル、ベンゾインブチルエーテル、ベンゾフェノン、
ｄ、ｌ−カンフアキノンを添加することにより、高感度
な光硬化性の樹脂となる。In addition to the above-mentioned physical properties as a cured product, the compound of the present invention has the excellent feature that it is a liquid monomer at room temperature, has excellent compatibility with other monomers, and has the ability to form other olefinic double bonds. Copolymerization with monomers can also be performed at room temperature, and since the molecule contains an acryloxy or methacryloxy group as a polymerizable group, it can be cured using most polymerization methods. In addition, heating polymerization and room temperature polymerization are possible by using a peroxide-aromatic tertiary amine redox polymerization initiator.Furthermore, as a photopolymerization initiator or sensitizer, benzoin ethyl ether, benzoin butyl ether, benzophenone,
By adding d,l-camphuaquinone, a highly sensitive photocurable resin can be obtained.
［実施例］
以下、本発明を実施例により具体的に説明するが、本発
明はこれら実施例に限定されない。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
参ＪｄＭ１ ［２，２−ヒ０ス（４−ヒドロキシエト
キシフェニル）へキサフルオロ７＠口バンの合成コ
温度計、撹拌機、滴下ロートおよび還流式冷却器を取り
つけた５００■ｌ四つロフラスコに２．２−（４−ヒド
ロキシフェニル）へキサフルオロプロパン６７ｇ、水酸
化ナトリウム１８ｇおよび蒸留水１５０ｍ Ａを入れ、
撹拌しながら温水浴で６０℃前後に１時間加温した０滴
下ロートよりエチレンクロルヒドリン３６ｇを撹拌下約
４０分かけ滴下した。さらに約８５℃で２時間撹拌後、
冷却した。フラスコ底部に分離した油状物をジエチルエ
ーテルで溶解抽出し、蒸留水で十分洗浄後、無水硫酸ナ
トリウムで１晩乾燥した。エーテルをエバポレータで留
去し、残留分として７８ｇの２．２−ビス（４−ヒドロ
キシエトキシフェニル）へキサフルオロプロパンを得た
。Reference JdM1 [2,2-hyos(4-hydroxyethoxyphenyl) hexafluoro 7@Ban's synthesis] 2 ml in a 500 l four-loop flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser. .Pour 67 g of 2-(4-hydroxyphenyl)hexafluoropropane, 18 g of sodium hydroxide and 150 m of distilled water,
While stirring, 36 g of ethylene chlorohydrin was added dropwise over about 40 minutes through a dropping funnel that had been heated to around 60°C in a hot water bath for 1 hour. After further stirring at approximately 85°C for 2 hours,
Cooled. The oily substance separated at the bottom of the flask was dissolved and extracted with diethyl ether, thoroughly washed with distilled water, and then dried over anhydrous sodium sulfate overnight. The ether was distilled off using an evaporator to obtain 78 g of 2.2-bis(4-hydroxyethoxyphenyl)hexafluoropropane as a residue.
実ｍ１Ｍ１ ［２，２−ヒ゛ス（４−メタクリロキシ
エトキシフェニル）〜キサフルオロ７°Ｄハ０ンの合成
］
温度計および還流冷却器を取りつけた５００ｍ ４１の
二つ目フラスコに参考例１で合成した２、２−ビス（４
−ヒドロキシエトキシフェニル）へキサフルオロプロパ
ン７８ｇ、メタクリル酸４８ｇ、Ｐ−）−ルエンスルホ
ン酸４ｇ、ピクリン酸０．２５ｇおよびトルエン３５０
■ｌを加え、２４時間還流させた。その間、連続抽出器
を使用して発生する水を反応系外へ排出した。冷却後、
２Ｎ−水酸化ナトリウム水溶液２００■ｌを加え、中和
、洗浄後蒸留水で十分洗浄し、無水硫酸ナトリウムで１
晩乾燥した。トルエンを減圧蒸留で留去し、淡褐色透明
な油状物として目的物８７ｇを得た。Actual m1M1 [Synthesis of 2,2-hys(4-methacryloxyethoxyphenyl)-xafluoro7°D] Synthesized in Reference Example 1 in a second flask of 500 m 41 equipped with a thermometer and a reflux condenser. 2,2-bis(4
-hydroxyethoxyphenyl)hexafluoropropane 78 g, methacrylic acid 48 g, P-)-luenesulfonic acid 4 g, picric acid 0.25 g and toluene 350 g
1 liter was added and the mixture was refluxed for 24 hours. During that time, water generated was discharged from the reaction system using a continuous extractor. After cooling,
Add 200 μl of 2N sodium hydroxide aqueous solution, neutralize, wash thoroughly with distilled water, and add 1 ml of anhydrous sodium sulfate.
Dry overnight. Toluene was distilled off under reduced pressure to obtain 87 g of the desired product as a pale brown transparent oil.
生成物は赤外線吸収スペクトルおよびプロトン核磁気共
鳴スペクトルにより目的物であることを確認した。以下
にその分析結果を示した。The product was confirmed to be the desired product by infrared absorption spectrum and proton nuclear magnetic resonance spectrum. The analysis results are shown below.
赤外線吸収スペクトル（液膜法）
３１００ 、３０５０ ｃｍ（芳香族ＶＣ−）ｔ）
１７２５ ｃｍ （エステル結合のνｃ＝ｏ
）１６４０ ｃｍ （オレフィンのνＣ＝Ｃ
）１６１３ 、１５１５ ｃｍ（芳香族νｃ＝ｃ）
’Ｈ−ＮＭＲ（溶媒： ＣＤＣｌ、 、内部標準： Ｔ
ＭＳ）δ＝、１．９５ｐｐ■（メチル基プロトン６Ｈ）
δ ＝４．２２〜４．２６ρρ謹（−０−ＣＩ、−ＣＨ
２−０−のメチレン７１トン４Ｈ）δ ＝４．４８〜４
．５２ＰＰ■（−０−Ｃ）Ｉ２−ＣＩ、−０−のメチレ
ン７１トン４Ｈ）δ＝ ５．５９ｐｐ■（末端ビニル基
のプロトン２Ｈ）δ＝ ６．１３ｐｐｍ（末端ビニル基
のプロトン２Ｈ）δ＝６．８８〜６．９２ｐｐｍ（芳香
族プロトン４）１）δ＝７．２６〜７．３２ｐｐ腫（芳
香族プロトン４Ｈ）実施例２，３、比較例１〜４
実施例１で得た化合物（Ｂｉｓ−ＭＥＰＨＦＰと略す）
およびこの重合体の各種物性を測定しな、比較のためフ
ッ素を含有していないビスフェノール骨格を有するジメ
タクリレートとしてＢｉｓ−ＧＭＡ（２，２−ビス−［
４−（２’−ヒドロキシ−３′−メタクリロキシプロポ
キシ）フェニル］プロパンおよびＢｉｓ−ＭＥＰＰ （
２，２−ビス（４−メタクリロキシエトキシフェニル）
プロパン）、脂肪族系ジメタクリレートとしてＴＥＧＤ
ＭＡ （トリーエチレングリコールジメタクリレート）
およびＵＤＭＡ （ジ−２＝メタクリロキシエチル−２
，２，４トリメチルへキサメチレンシカ−バメート）に
ついても同様の測定を行った。使用モノマーの組成は次
のとおりである。Infrared absorption spectrum (liquid film method) 3100, 3050 cm (aromatic VC-)t)
1725 cm (νc=o of ester bond
)1640 cm (νC=C of olefin
) 1613, 1515 cm (aromatic νc=c)
'H-NMR (solvent: CDCl, internal standard: T
MS) δ=, 1.95pp■ (methyl group proton 6H)
δ = 4.22~4.26ρρ(-0-CI,-CH
71 tons of 2-0-methylene 4H) δ = 4.48~4
．． 52PP ■ (-0-C) I2-CI, -0- methylene 71 tons 4H) δ = 5.59 pp ■ (Proton 2H of terminal vinyl group) δ = 6.13 ppm (Proton 2H of terminal vinyl group) δ = 6.88-6.92 ppm (aromatic proton 4) 1) δ = 7.26-7.32 ppm (aromatic proton 4H) Examples 2, 3, Comparative Examples 1-4 Compound obtained in Example 1 ( (abbreviated as Bis-MEPHFP)
And various physical properties of this polymer were measured.For comparison, Bis-GMA (2,2-bis-[
4-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane and Bis-MEPP (
2,2-bis(4-methacryloxyethoxyphenyl)
propane), TEGD as aliphatic dimethacrylate
MA (triethylene glycol dimethacrylate)
and UDMA (di-2=methacryloxyethyl-2
, 2,4 trimethylhexamethylene cicabamate). The composition of the monomers used is as follows.
実施例２ Ｂｉｓ−ＭＥＰＨＦＰ ＝ １０
０ｍｏ１％１） ３ Ｂｉｓ−ＭＥＰＨＦ
Ｐ：ＴＥＧＤＭＡ ＝５０：５０ｍｏ１％比較例Ｉ
Ｂｉｓ−ＧＭＡ ：ＴＥＧＤＭＡ ＝５０：５０ｇ
＋ｏ１％７／ ２ ＢｉｓＭＥＰＰ ：ＴＥＧＤ
ＭＡ ＝５０：５０ｍｏ１％Ｈ３ＢｉｓＭＥＰＰ
：ＴＥＧＤＭＡ ＝３０ニア０ｓｏｌ ％ツノ
４ ＵＤＭＡ
＝１００ 鳳０１％なお、重合体は各組成のモノマー
に過酸化ベンゾイルを０．５重量％加え、６０”Ｃで２
４時間、９ｏで２４時間、１２０℃で２４時間加熱重合
したバルク重合体を使用した。Example 2 Bis-MEPHFP = 10
0mo1%1) 3 Bis-MEPHF
P:TEGDMA =50:50mo1% Comparative Example I
Bis-GMA:TEGDMA =50:50g
+o1%7/2 BisMEPP:TEGD
MA = 50:50mo1%H3BisMEPP
:TEGDMA = 30 near 0sol %horn
4 UDMA
= 100 01% The polymer was prepared by adding 0.5% by weight of benzoyl peroxide to the monomers of each composition and heating it at 60"C for 2
A bulk polymer was used which was heat-polymerized for 4 hours, at 9o C. for 24 hours, and at 120.degree. C. for 24 hours.
■屈折率
屈折率はアツベ屈折計を用い、重合体の測定に際しては
中間液としてα−ブロモナフタレンを使用した。(2) Refractive Index The refractive index was measured using an Atsube refractometer, and α-bromonaphthalene was used as an intermediate liquid when measuring the polymer.
■重合体の吸水量、溶解量
重合体（直径２０ｍｍ、厚さ０．５ｍｍ ｆ）円板状）
を８０℃で真空乾燥し、恒量とした後、３７℃蒸留水中
に２０日間浸漬後、吸水による重量増加分を表面積で除
し、吸水量を求めた。さらにこの試料を８０’Ｃで真空
乾燥し恒量とした時の重量減少分を表面積で除し、溶解
量を求めた。■Water absorption and dissolution amount of polymer Polymer (diameter 20mm, thickness 0.5mm f) disk shape)
After vacuum drying at 80° C. to a constant weight, the sample was immersed in distilled water at 37° C. for 20 days, and the amount of water absorbed was determined by dividing the weight increase due to water absorption by the surface area. Further, this sample was vacuum dried at 80'C to give a constant weight, and the weight loss was divided by the surface area to determine the amount dissolved.
■重合体の圧縮強度
重合体（直径４ｍｍ 、長さ６ｍｍの円柱状）をオート
グラフを使用して、クロスヘツドスピード０．５鳳鳳／
諺ｉｎで測定した。試料は圧縮応力に対して大きな塑性
変形を起こした後、破壊するため、圧縮特性は圧縮比例
限および破断強さの両者により評価した。これらの結果
を第１表に示した。■ Compressive Strength of Polymer Using an autograph, measure a polymer (cylindrical shape with a diameter of 4 mm and a length of 6 mm) at a crosshead speed of 0.5 /
Measured by the proverb. Since the sample breaks after undergoing large plastic deformation in response to compressive stress, the compressive properties were evaluated by both the compressive proportional limit and the breaking strength. These results are shown in Table 1.
第１表
［発明の効果］
本発明の化合物は含フッ素ビスフェノール基を骨格とす
るジアクリレートおよびジメタクリレートであり、屈折
率が低く、しかも常温で液状であり、他の各種モノマー
との相溶性も良いため、各種高分子架橋剤としても広く
使用できる。また、得られる重合体は屈折率が低く、さ
らに強度、耐水性等の物性に優れるため、光学材料、歯
科材料、機能性高分子材料等として幅広い分野での応用
が可能である。Table 1 [Effects of the Invention] The compounds of the present invention are diacrylates and dimethacrylates having a fluorine-containing bisphenol group as a skeleton, and have a low refractive index, are liquid at room temperature, and are compatible with various other monomers. Because of its good properties, it can be widely used as various polymer crosslinking agents. Furthermore, the obtained polymer has a low refractive index and excellent physical properties such as strength and water resistance, so it can be applied in a wide range of fields such as optical materials, dental materials, and functional polymer materials.
特許出願人 セントラル硝子株式会社Patent applicant: Central Glass Co., Ltd.
Claims (2)
される含フッ素ビスフェノール基を骨格とするジアクリ
レートまたはジメタクリレート。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R represents a hydrogen atom or a methyl group.) Diacrylate or dimethacrylate whose skeleton is a fluorine-containing bisphenol group.
ル基を骨格とするジアクリレートまたはジメタクリレー
トを成分とする高分子材料。(2) A polymer material whose component is diacrylate or dimethacrylate having a skeleton of a fluorine-containing bisphenol group represented by the general formula (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6028888A JPH0674235B2 (en) | 1988-03-16 | 1988-03-16 | Diacrylate or dimethacrylate having fluorinated bisphenol group as skeleton and polymer material containing these |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6028888A JPH0674235B2 (en) | 1988-03-16 | 1988-03-16 | Diacrylate or dimethacrylate having fluorinated bisphenol group as skeleton and polymer material containing these |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01238553A true JPH01238553A (en) | 1989-09-22 |
| JPH0674235B2 JPH0674235B2 (en) | 1994-09-21 |
Family
ID=13137818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6028888A Expired - Fee Related JPH0674235B2 (en) | 1988-03-16 | 1988-03-16 | Diacrylate or dimethacrylate having fluorinated bisphenol group as skeleton and polymer material containing these |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674235B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030013879A (en) * | 2001-08-09 | 2003-02-15 | 최동훈 | Photo-reactive di(meth)acrylate derivative and its preparation method thereof |
| KR100740994B1 (en) * | 2006-03-30 | 2007-07-20 | 한국화학연구원 | Crosslinkable perfluorinated di(metha)acrylate compounds and their photopolymer composite and photopolymer film using them |
| JP2013216599A (en) * | 2012-04-06 | 2013-10-24 | Yamahachi Shizai Kogyo Kk | Dental composition and artificial tooth |
| WO2016031249A1 (en) * | 2014-08-26 | 2016-03-03 | 株式会社ニコン | Resin precursor composition for optical materials, optical element obtained from said composition, and diffractive optical element configured using said optical element |
-
1988
- 1988-03-16 JP JP6028888A patent/JPH0674235B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030013879A (en) * | 2001-08-09 | 2003-02-15 | 최동훈 | Photo-reactive di(meth)acrylate derivative and its preparation method thereof |
| KR100740994B1 (en) * | 2006-03-30 | 2007-07-20 | 한국화학연구원 | Crosslinkable perfluorinated di(metha)acrylate compounds and their photopolymer composite and photopolymer film using them |
| JP2013216599A (en) * | 2012-04-06 | 2013-10-24 | Yamahachi Shizai Kogyo Kk | Dental composition and artificial tooth |
| WO2016031249A1 (en) * | 2014-08-26 | 2016-03-03 | 株式会社ニコン | Resin precursor composition for optical materials, optical element obtained from said composition, and diffractive optical element configured using said optical element |
| JPWO2016031249A1 (en) * | 2014-08-26 | 2017-06-08 | 株式会社ニコン | Resin precursor composition for optical material, optical element obtained from the composition, and diffractive optical element formed using the optical element |
| EP3187907A4 (en) * | 2014-08-26 | 2018-03-14 | Nikon Corporation | Resin precursor composition for optical materials, optical element obtained from said composition, and diffractive optical element configured using said optical element |
| US10577446B2 (en) | 2014-08-26 | 2020-03-03 | Nikon Corporation | Resin precursor composition for optical materials, optical element obtained from the composition, and diffractive optical element configured using the optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0674235B2 (en) | 1994-09-21 |
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