JP2004339155A - Methyl methacrylate-based composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new norbornane compound contributing to improvement of physical properties (heat resistance, chemical resistance, water absorbing property, rigidity, etc.) of a conventional transparent methacrylic resin, a composition containing the compound and a methyl methacrylate-based polymer obtained by polymerizing the composition. <P>SOLUTION: The composition comprises (A) methyl methacrylate and/or methyl methacrylate polymer and (B) a compound represented by general formula (1) [wherein R<SB>1</SB>and R<SB>2</SB>are each independently either one group selected from groups represented by general formula (2) and general formula (3) (wherein R<SB>3</SB>to R<SB>6</SB>are each independently a hydrogen atom, a methyl group or an ethyl group)]. Methacrylic resin remarkably improved in heat resistance, stiffness and water absorption property and/or chemical resistance while maintaining transparency can be obtained, compared with a case when methyl methacrylate is alone used by using a methyl methacrylate-based composition containing a norbornane compound represented by general formula (1). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【０００７】
〔式中、Ｒ_１およびＲ_２は、それぞれ独立に、式（２）または式（３）
【０００８】
【化１１】

【０００９】
【化１２】

【００１０】
（式中、Ｒ_３〜Ｒ_６は、それぞれ独立に、水素原子、メチル基、またはエチル基を表す）で表されるいずれかの基である。〕
▲２▼ （Ｂ）ノルボルナン化合物が一般式（４）で表される化合物である▲１▼記載の組成物
【００１１】
【化１３】

【００１２】
［式中、Ｒ_８、Ｒ_９のいずれか一方およびＲ_７は式（２）で表される基であり、Ｒ_８、Ｒ_９のうち、もう一方は水素原子を表す。］
▲３▼ （Ｂ）ノルボルナン化合物が一般式（５）で表される化合物である▲１▼記載の組成物
【００１３】
【化１４】

【００１４】
［式中、Ｒ_１０およびＲ_１１は、前記式（３）で表されるの基である。］
▲４▼ ▲１▼〜▲３▼いずれかに記載の組成物を重合してなる重合体
▲５▼ ▲４▼記載の重合体からなる光学部品（ディスプレイ部材、導光板・拡散板、スクリーン板、レンズなど）
▲６▼ 前記一般式（４）で表される化合物
▲７▼ 前記一般式（５）で表される化合物
に関する。
【００１５】
【発明の実施の形態】
本発明は、前記一般式（１）で表されるノルボルナン化合物および該化合物を含有する組成物、ならびに該組成物を重合してなる重合体に関するものである。一般式（１）で表されるノルボルナン化合物の具体例としては、以下の構造式で示される化合物が挙げられるが、これらに限定されるわけではない。
【００１６】
【化１５】

【００１７】
【化１６】

【００１８】
【化１７】

【００１９】
本発明の一般式（１）で表されるノルボルナン化合物は、ノルボルナン−ジ−酸クロライド（以下、ＮＢＤＣ）と、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシ−１，３−ジ（メタ）アクリロイルオキシプロパン、２−ヒドロキシ−３−アクリロイルオキシプロピルメタクリレート等のアクリレート化合物とを、塩基の存在下または非存在下において、溶媒中で反応させることにより得ることができる。このとき用いる塩基としては、例えば、ピリジン、トリエチルアミン、ピペリジン等が挙げられる。溶媒としては、原料類と反応性を有しない溶媒であり、例えば、ヘキサン、クロロホルム、ベンゼン、トルエン等が用いられる。
【００２０】
反応の際のＮＢＤＣとアクリレート化合物との割合は、ＮＢＤＣ１モルに対し、アクリレート化合物１．５〜５モル、好ましくは１．８〜３モルである。反応は、アクリレート化合物と溶媒の混合液にＮＢＤＣを滴下し、塩基の存在下または非存在下で行われる。反応温度は９０℃以下、好ましくは０〜５０℃である。塩基の使用量は、ＮＢＤＣ１モルに対し０．５〜５モル、好ましくは１〜３モルである。
【００２１】
反応終了後、反応の際に塩基を用いなかった場合は反応液をそのまま濃縮することにより、塩基を用いた場合はその塩酸塩を濾過などにより除去したのちに濃縮することにより、本発明のノルボルナン化合物を得ることが出来る。また、カラムクロマトグラフィー等の方法を行うことにより、より高純度のものを得ることもできる。
なお、一般式（１）で表されるノルボルナン化合物の製造方法は、これらに限定されるわけではない。
【００２２】
本発明のメタクリル酸メチル系組成物に含まれる一般式（１）で表されるノルボルナン化合物のうち好ましいものは、合成コスト（原料ＮＢＤＣのコストなど）の観点から、Ｒ_１の結合位置をビシクロ環の２位とした場合のＲ_２の結合位置が５位または６位の化合物である。
【００２３】
本発明の一般式（１）で表されるノルボルナン化合物を含むメタクリル酸メチル系組成物、該組成物を重合してなる重合体、および、一般式（１）で表されるノルボルナン化合物は、光および熱硬化樹脂、塗料、接着剤、インキなどの原料または製品として有用である。また、光学部品（ディスプレイ部材、導光板・拡散板、スクリーン板、レンズなど）をはじめ、特に透明性、耐熱性、耐薬品性、低吸水性、および剛性を必要とする用途にはとりわけ有用である。
【００２４】
【実施例】
以下に本発明を実施例により具体的に説明するが、本発明はこれらにより何等限定されるものではない。なお、実施例中の「部」は「重量部」を表す。
なお、実施例中での樹脂板の物性などの評価は以下のようにして行った。
・重合の容易性
暴走反応（ワカメ現象：樹脂表面が樹皮状を呈し乱れる現象）の有無および程度を、以下の基準により目視にて判定した。
○：発生しない
△：部分的に発生
×：全面に発生
・耐熱性
リガク（株）のＴＭＡ分析装置でＴｇを測定した。
・剛性
ＪＩＳ Ｋ７１７１法で曲げ試験を行い、曲げ弾性率を測定した。
・吸水率
ＡＳＴＭ Ｄ５７０法で吸水性を試験し、吸水率を測定した。
・耐薬品性
ＪＩＳ Ｋ７１１４法で、アセトン、トルエン、および、１０％カセイソーダ水の各々について試験を行い、以下の基準により目視にて判定した。
○：異常なし
△：膨潤またはクラックがみられる
×：溶解する
【００２５】
実施例１
２−ヒドロキシエチルメタアクリレート１７．７部、ピリジン１０．７部、トルエン７０部を混合し、反応温度を０〜２０℃に保ちながら、式（６）と式（７）で表されるＮＢＤＣの約４／６混合物１０．０部を３０分かけて滴下装入し、さらに１０〜３０℃で８時間撹拌した。その後、生じた白色結晶をろ過により除去し、得られたろ液を塩酸水および水で洗浄した。次いでこの液を濃縮し、シリカゲルカラムクロマトグラフ法により精製し、式（８）で示される化合物と式（９）で示される化合物の混合物１４．１部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：４０８ 測定値：４０８
【００２６】
【化１８】

【００２７】
実施例２
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシプロピルメタアクリレート１９．６部に代える以外は、実施例１と同様にして、式（１０）で示される化合物と式（１１）で示される化合物の混合物１７．６部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：４３６ 測定値：４３６
【００２８】
【化１９】

【００２９】
実施例３
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシエチルアクリレート１５．７部に代える以外は、実施例１と同様にして、式（１２）で示される化合物と式（１３）で示される化合物の混合物１５．０部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：３８０ 測定値：３８０
【００３０】
【化２０】

【００３１】
実施例４
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシプロピルアクリレート１７．７部に代える以外は、実施例１と同様にして、式（１４）で示される化合物と式（１５）で示される化合物の混合物１６．３部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：４０８ 測定値：４０８
【００３２】
【化２１】

【００３３】
実施例５
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシ−１，３−ジメタアクリロイルオキシプロパン３１．０部に代える以外は、実施例１と同様にして、式（１６）で示される化合物と式（１７）で示される化合物の混合物２２．８部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：６０４ 測定値：６０４
【００３４】
【化２２】

【００３５】
実施例６
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシ−１，３−ジアクリロイルオキシプロパン２７．２部に代える以外は、実施例１と同様にして、式（１８）で示される化合物と式（１９）で示される化合物の混合物２０．１部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：５４８ 測定値：５４８
【００３６】
【化２３】

【００３７】
実施例７
実施例１の２−ヒドロキシエチルメタアクリレート１７．７部を、２−ヒドロキシエチルメタアクリレート６．５部と２−ヒドロキシプロピルメタアクリレート７．２部の混合物に代える以外は、実施例１と同様にして、式（２０）で示される化合物と式（２１）で示される化合物の混合物１１．０部を得た。得られた化合物は元素分析およびＦＤ−ＭＳ分析により確認した。
・元素分析値

・ＦＤ−ＭＳ （ｍ／ｚ）
計算値：４２２ 測定値：４２２
【００３８】
【化２４】

【００３９】
実施例８
メタクリル酸メチル１００部と、実施例２で製造した式（１０）で表される化合物と式（１１）で表される化合物の混合物１０部を混合し、そこにラジカル反応開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート０．２部を添加混合し、その後脱気し、組成物を調製した。
この組成物を、対面した一辺が２００ｍｍの正方形ガラス板２枚の間に塩化ビニール製のガスケットを配した、空間距離が２ｍｍの注型重合用鋳型に注入した。その後、熱風循環乾燥機で最初に７０℃で２時間加熱し、次に７０℃から１３０℃まで２時間かけて昇温し、最後に１３０℃で１時間加熱して重合を行った。重合中に異常は認められなかった。その後、室温まで冷却し、脱型して、厚さ２ｍｍの無色透明な樹脂板を得た。
該樹脂板の評価結果は以下の通りであった。
・重合の容易性：○
・耐熱性：Ｔｇ＝１３６℃
・剛性：曲げ弾性率＝３．１ＧＰａ
・吸水率：０．４９％
・耐薬品性：アセトン△（膨潤）、トルエン○、１０％カセイソーダ水○
【００４０】
実施例９
式（１０）で表される化合物と式（１１）で表される化合物の混合物１０部を、実施例１で製造した式（８）で表される化合物と式（９）で表される化合物の混合物１０部に代える以外は、実施例８の方法に従い組成物を調製した。
この組成物を、実施例８の方法に従い、鋳型中で注型重合した。重合中に異常は認められなかった。その後、室温まで冷却し、脱型して、厚さ２ｍｍの無色透明な樹脂板を得た。
該樹脂板の評価結果は以下の通りであった。
・重合の容易性：○
・耐熱性：Ｔｇ＝１３４℃
・剛性：曲げ弾性率＝３．０ＧＰａ
・吸水率：０．４９％
・耐薬品性：アセトン△（膨潤）、トルエン○、１０％カセイソーダ水○
【００４１】
実施例１０
三菱レイヨン（株）製メタクリル酸メチルシラップＳＹ−１０２Ｃを８０部、メタクリル酸メチル２０部、および、実施例１で製造した式（８）で表される化合物と式（９）で表される化合物の混合物１０部を混合し、そこにラジカル反応開始剤としてｔ−ブチルパーオキシ−２−エチルヘキサノエート０．２部を添加混合し、その後脱気し、組成物を調製した。
この組成物を、実施例８の方法に従い、鋳型中で注型重合した。重合中に異常は認められなかった。その後、室温まで冷却し、脱型して、厚さ２ｍｍの無色透明な樹脂板を得た。
該樹脂板の評価結果は以下の通りであった。
・重合の容易性：○
・耐熱性：Ｔｇ＝１３５℃
・剛性：曲げ弾性率＝３．１ＧＰａ
・吸水率：０．５１％
・耐薬品性：アセトン△（膨潤）、トルエン○、１０％カセイソーダ水○
【００４２】
比較例
メタクリル酸メチル１００部とｔ−ブチルパーオキシ−２−エチルヘキサノエート０．２部を混合し、その後脱気して組成物を調製した。この組成物を実施例８の方法に従い、鋳型中で注型重合した。重合中に異常は認められなかった。その後、室温まで冷却し、脱型して、厚さ２ｍｍの無色透明な樹脂板を得た。
該樹脂板の評価結果は以下の通りであった。その結果、以下の評価結果のように、耐熱性、剛性、耐薬品性が、実施例８〜１０の樹脂板と比較して著しく劣っていた。
・重合の容易性：○
・耐熱性：Ｔｇ＝１０５℃
・剛性：曲げ弾性率＝２．７ＧＰａ
・吸水率：０．５４％
・耐薬品性：アセトン×、トルエン×、１０％カセイソーダ水○
【００４３】
【発明の効果】
本発明の一般式（１）で表されるノルボルナン化合物を含むメタクリル酸メチル系組成物を用いれば、メタクリル酸メチルを単独で用いるよりも、透明性を維持しつつ、耐熱性、剛性、低吸水性、および／または耐薬品性を大幅に向上したメタクリル樹脂を得ることが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a methyl methacrylate composition, a methyl methacrylate polymer, and a polymerizable compound.
[0002]
[Prior art]
The advantages of methacrylic resin, which is widely used as a transparent member and is also useful as a raw material for light and thermosetting resins, paints, adhesives, inks, etc., are excellent in transparency and light resistance, and have good balance with mechanical properties, In addition, processing is good. However, as for glazing materials, display members, light guide plates / diffusion plates, screen plates, or members such as optical lenses, the demand for physical properties of methacrylic resin or its alternative resin is also diversified, and for current resins, for example, Improvements in heat resistance, chemical resistance, water absorption, rigidity, impact resistance, and the like are required.
[0003]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a novel norbornane compound and a composition containing the compound, which contribute to improvement of various physical properties (heat resistance, chemical resistance, water absorption, rigidity, etc.) of the conventional transparent methacrylic resin, Another object of the present invention is to provide a methyl methacrylate polymer obtained by polymerizing the composition.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, a methyl methacrylate-based composition containing a norbornane compound having a specific structure, a polymer obtained by polymerizing the composition is suitable for the above object. Thus, the present invention has been completed.
[0005]
That is, the present invention
(1) A composition comprising (A) methyl methacrylate and / or a polymer of methyl methacrylate and (B) a norbornane compound represented by the general formula (1).
[0006]
Embedded image

[0007]
[Wherein, R ₁ and R ₂ are each independently a formula (2) or a formula (3)
[0008]
Embedded image

[0009]
Embedded image

[0010]
(Wherein, R _{3 to} R ₆ each independently represent a hydrogen atom, a methyl group, or an ethyl group). ]
(2) The composition according to (1), wherein the (B) norbornane compound is a compound represented by the general formula (4).
Embedded image

[0012]
[In the formula, one of R ₈ and R ₉ and R ₇ are groups represented by the formula (2), and the other one of R ₈ and R ₉ represents a hydrogen atom. ]
(3) The composition according to (1), wherein the (B) norbornane compound is a compound represented by the general formula (5):
Embedded image

[0014]
[Wherein, R ₁₀ and R ₁₁ are groups represented by the above formula (3). ]
(4) A polymer obtained by polymerizing the composition described in any one of (1) to (3). (5) An optical component (display member, light guide plate / diffusion plate, screen plate) made of the polymer described in (4). , Lens, etc.)
(6) The compound represented by the general formula (4). (7) The compound represented by the general formula (5).
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a norbornane compound represented by the general formula (1), a composition containing the compound, and a polymer obtained by polymerizing the composition. Specific examples of the norbornane compound represented by the general formula (1) include, but are not limited to, compounds represented by the following structural formulas.
[0016]
Embedded image

[0017]
Embedded image

[0018]
Embedded image

[0019]
The norbornane compound represented by the general formula (1) of the present invention includes norbornane-di-acid chloride (hereinafter, NBDC), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy It can be obtained by reacting an acrylate compound such as -1,3-di (meth) acryloyloxypropane and 2-hydroxy-3-acryloyloxypropyl methacrylate in a solvent in the presence or absence of a base. it can. Examples of the base used at this time include pyridine, triethylamine, piperidine and the like. The solvent is a solvent having no reactivity with the raw materials, for example, hexane, chloroform, benzene, toluene and the like are used.
[0020]
The ratio of NBDC to the acrylate compound in the reaction is 1.5 to 5 mol, preferably 1.8 to 3 mol, per 1 mol of NBDC. The reaction is carried out in the presence or absence of a base by dropping NBDC to a mixture of an acrylate compound and a solvent. The reaction temperature is 90 ° C or lower, preferably 0 to 50 ° C. The amount of the base to be used is 0.5 to 5 mol, preferably 1 to 3 mol, per 1 mol of NBDC.
[0021]
After completion of the reaction, the norbornane of the present invention can be obtained by concentrating the reaction solution as it is when no base is used in the reaction, or by removing the hydrochloride thereof by filtration or the like when using a base. A compound can be obtained. Further, by performing a method such as column chromatography, a higher purity product can be obtained.
The method for producing the norbornane compound represented by the general formula (1) is not limited to these.
[0022]
Among the norbornane compounds represented by the general formula (1) contained in the methyl methacrylate-based composition of the present invention, preferred are those in which the bond position of R ₁ is a bicyclo ring from the viewpoint of synthesis cost (eg, cost of raw material NBDC). Is a compound in which the bonding position of R ₂ is the 5-position or the 6-position in the case of the _2- position.
[0023]
The methyl methacrylate-based composition containing the norbornane compound represented by the general formula (1) of the present invention, a polymer obtained by polymerizing the composition, and the norbornane compound represented by the general formula (1) are: It is also useful as a raw material or product for thermosetting resins, paints, adhesives, inks and the like. It is especially useful for applications that require transparency, heat resistance, chemical resistance, low water absorption, and rigidity, including optical components (display members, light guide plates / diffusion plates, screen plates, lenses, etc.). is there.
[0024]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the examples, “parts” represents “parts by weight”.
The evaluation of the physical properties of the resin plate in the examples was performed as follows.
Ease of polymerization The presence or absence of runaway reaction (wakame phenomenon: a phenomenon in which the resin surface is bark-like and disturbed) was visually determined according to the following criteria.
：: Not generated △: Partially generated ×: Generated on the entire surface Tg was measured with a TMA analyzer of Rigaku Corporation.
-Rigidity A bending test was performed according to JIS K7171 method, and a bending elastic modulus was measured.
-Water absorption The water absorption was tested by the ASTM D570 method, and the water absorption was measured.
-Chemical resistance A test was performed for each of acetone, toluene, and 10% caustic soda water according to the JIS K7114 method, and visually judged according to the following criteria.
：: No abnormality △: Swelling or cracks observed X: Dissolved
Example 1
17.7 parts of 2-hydroxyethyl methacrylate, 10.7 parts of pyridine and 70 parts of toluene are mixed, and while maintaining the reaction temperature at 0 to 20 ° C., the NBDC represented by the formulas (6) and (7) is mixed. About 4/6 mixture 10.0 parts was added dropwise over 30 minutes, and the mixture was further stirred at 10 to 30 ° C. for 8 hours. Thereafter, the generated white crystals were removed by filtration, and the obtained filtrate was washed with aqueous hydrochloric acid and water. Next, this solution was concentrated and purified by silica gel column chromatography to obtain 14.1 parts of a mixture of a compound represented by the formula (8) and a compound represented by the formula (9). The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 408 Measured value: 408
[0026]
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[0027]
Example 2
A compound represented by the formula (10) and a compound represented by the formula (10) were prepared in the same manner as in Example 1 except that 17.7 parts of 2-hydroxyethyl methacrylate in Example 1 was replaced with 19.6 parts of 2-hydroxypropyl methacrylate. 17.6 parts of a mixture of the compounds represented by 11) were obtained. The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 436 Measured value: 436
[0028]
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[0029]
Example 3
A compound represented by the formula (12) and a compound represented by the formula (13) were prepared in the same manner as in Example 1 except that 17.7 parts of 2-hydroxyethyl methacrylate in Example 1 was replaced with 15.7 parts of 2-hydroxyethyl acrylate. 15.0 parts of a mixture of the compounds of the formula The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 380 Measured value: 380
[0030]
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[0031]
Example 4
A compound represented by the formula (14) and a compound represented by the formula (15) were prepared in the same manner as in Example 1 except that 17.7 parts of 2-hydroxyethyl methacrylate in Example 1 was replaced with 17.7 parts of 2-hydroxypropyl acrylate. 16.3 parts of a mixture of the compounds of the formula The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 408 Measured value: 408
[0032]
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[0033]
Example 5
The procedure of Example 1 was repeated, except that 17.7 parts of 2-hydroxyethyl methacrylate in Example 1 was replaced by 31.0 parts of 2-hydroxy-1,3-dimethacryloyloxypropane. And 22.8 parts of a mixture of a compound represented by the formula and a compound represented by the formula (17) were obtained. The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 604 Measured value: 604
[0034]
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[0035]
Example 6
In the same manner as in Example 1 except that 17.7 parts of 2-hydroxyethyl methacrylate in Example 1 was replaced with 27.2 parts of 2-hydroxy-1,3-diacryloyloxypropane, the formula (18) was used. 20.1 parts of a mixture of the compound represented by the formula (19) was obtained. The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 548 Measured value: 548
[0036]
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[0037]
Example 7
Except that 17.7 parts of 2-hydroxyethyl methacrylate of Example 1 was replaced with a mixture of 6.5 parts of 2-hydroxyethyl methacrylate and 7.2 parts of 2-hydroxypropyl methacrylate, the same procedure as in Example 1 was carried out. Thus, 11.0 parts of a mixture of a compound represented by the formula (20) and a compound represented by the formula (21) was obtained. The obtained compound was confirmed by elemental analysis and FD-MS analysis.
・ Elemental analysis value

・ FD-MS (m / z)
Calculated value: 422 Measured value: 422
[0038]
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[0039]
Example 8
100 parts of methyl methacrylate and 10 parts of a mixture of the compound represented by the formula (10) and the compound represented by the formula (11) prepared in Example 2 were mixed, and t-butyl was added thereto as a radical reaction initiator. 0.2 parts of peroxy-2-ethylhexanoate was added and mixed, followed by degassing to prepare a composition.
This composition was poured into a casting polymerization mold having a space distance of 2 mm, in which a gasket made of vinyl chloride was disposed between two square glass plates having sides of 200 mm facing each other. Thereafter, the mixture was first heated at 70 ° C. for 2 hours by a hot air circulating drier, then heated from 70 ° C. to 130 ° C. over 2 hours, and finally heated at 130 ° C. for 1 hour to perform polymerization. No abnormality was observed during the polymerization. Thereafter, the mixture was cooled to room temperature and demolded to obtain a colorless and transparent resin plate having a thickness of 2 mm.
The evaluation results of the resin plate were as follows.
-Ease of polymerization: ○
・ Heat resistance: Tg = 136 ° C
-Rigidity: Flexural modulus = 3.1 GPa
・ Water absorption: 0.49%
・ Chemical resistance: acetone △ (swelling), toluene ト ル エ ン, 10% caustic soda water ○
[0040]
Example 9
10 parts of a mixture of the compound represented by the formula (10) and the compound represented by the formula (11) were prepared by mixing the compound represented by the formula (8) and the compound represented by the formula (9) produced in Example 1. A composition was prepared according to the method of Example 8, except that 10 parts of the mixture was used.
This composition was cast polymerized in a mold according to the method of Example 8. No abnormality was observed during the polymerization. Thereafter, the mixture was cooled to room temperature and demolded to obtain a colorless and transparent resin plate having a thickness of 2 mm.
The evaluation results of the resin plate were as follows.
-Ease of polymerization: ○
・ Heat resistance: Tg = 134 ° C
-Rigidity: Flexural modulus = 3.0 GPa
・ Water absorption: 0.49%
・ Chemical resistance: acetone △ (swelling), toluene ト ル エ ン, 10% caustic soda water ○
[0041]
Example 10
80 parts of methyl methacrylate SY-102C manufactured by Mitsubishi Rayon Co., Ltd., 20 parts of methyl methacrylate, and the compound represented by formula (8) and the compound represented by formula (9) produced in Example 1 Was mixed, and 0.2 part of t-butylperoxy-2-ethylhexanoate was added and mixed as a radical reaction initiator, followed by degassing to prepare a composition.
This composition was cast polymerized in a mold according to the method of Example 8. No abnormality was observed during the polymerization. Thereafter, the mixture was cooled to room temperature and demolded to obtain a colorless and transparent resin plate having a thickness of 2 mm.
The evaluation results of the resin plate were as follows.
-Ease of polymerization: ○
Heat resistance: Tg = 135 ° C
-Rigidity: Flexural modulus = 3.1 GPa
・ Water absorption: 0.51%
・ Chemical resistance: acetone △ (swelling), toluene ト ル エ ン, 10% caustic soda water ○
[0042]
Comparative Example 100 parts of methyl methacrylate and 0.2 part of t-butylperoxy-2-ethylhexanoate were mixed, followed by degassing to prepare a composition. This composition was cast polymerized in a mold according to the method of Example 8. No abnormality was observed during the polymerization. Thereafter, the mixture was cooled to room temperature and demolded to obtain a colorless and transparent resin plate having a thickness of 2 mm.
The evaluation results of the resin plate were as follows. As a result, as shown in the following evaluation results, heat resistance, rigidity, and chemical resistance were significantly inferior to those of the resin plates of Examples 8 to 10.
-Ease of polymerization: ○
Heat resistance: Tg = 105 ° C
-Rigidity: Flexural modulus = 2.7 GPa
・ Water absorption: 0.54%
・ Chemical resistance: acetone x, toluene x, 10% caustic soda water
[0043]
【The invention's effect】
The use of the methyl methacrylate-based composition of the present invention containing the norbornane compound represented by the general formula (1) maintains heat resistance, rigidity, and low water absorption, compared with the case of using methyl methacrylate alone. A methacrylic resin having significantly improved properties and / or chemical resistance can be obtained.

Claims (7)

A composition comprising (A) methyl methacrylate and / or a polymer of methyl methacrylate and (B) a norbornane compound represented by the general formula (1).

[Wherein, R ₁ and R ₂ are each independently a formula (2) or a formula (3)

(Wherein, R _{3 to} R ₆ each independently represent a hydrogen atom, a methyl group, or an ethyl group). ] The composition according to claim 1, wherein the (B) norbornane compound is a compound represented by the general formula (4).

[In the formula, one of R ₈ and R ₉ and R ₇ are groups represented by the formula (2), and the other one of R ₈ and R ₉ represents a hydrogen atom. ] The composition according to claim 1, wherein (B) the norbornane compound is a compound represented by the general formula (5).

[Wherein, R ₁₀ and R ₁₁ are groups represented by the formula (3). ] A polymer obtained by polymerizing the composition according to claim 1. An optical component comprising the polymer according to claim 4. A compound represented by the general formula (4).

[Wherein, one of R ₈ and R ₉ and R ₇ are those represented by formula (2)

(Wherein, R ₃ and R ₄ each independently represent a hydrogen atom, a methyl group, or an ethyl group), and the other one of R ₈ and R ₉ represents a hydrogen atom . ] A compound represented by the general formula (5).

[Wherein R ₁₀ and R ₁₁ are represented by the formula (3)

(Wherein, R ₅ and R ₆ each independently represent a hydrogen atom, a methyl group, or an ethyl group). ]