JPH07206934A - Polyfunctional monomer and its polymer - Google Patents
Polyfunctional monomer and its polymerInfo
- Publication number
- JPH07206934A JPH07206934A JP6001485A JP148594A JPH07206934A JP H07206934 A JPH07206934 A JP H07206934A JP 6001485 A JP6001485 A JP 6001485A JP 148594 A JP148594 A JP 148594A JP H07206934 A JPH07206934 A JP H07206934A
- Authority
- JP
- Japan
- Prior art keywords
- polyfunctional monomer
- imide
- chemical
- organic residue
- polymer
- 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.)
- Pending
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/40—Imides, e.g. cyclic imides
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は半導体パッケージ，プリ
ント板の含浸樹脂，レジスト材等の耐熱性が要求される
各種絶縁材料に適した硬化物を与える多官能モノマとそ
の重合体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyfunctional monomer and a polymer thereof which gives a cured product suitable for various insulating materials such as semiconductor packages, impregnated resins for printed boards, resist materials and the like, which require heat resistance.
【０００２】[0002]
【従来の技術】従来、耐熱性の優れた樹脂としてはポリ
イミドが知られている。しかし、ポリイミド自体は溶解
性，溶融性に乏しいためその使用範囲が限定される。こ
れに代わる耐熱材料は高分子論文集第３７巻４号１９９
〜２０６ページ，特開昭61−145225号，特開平2−21251
2 号に記載の種々のポリマレイミドや多くの多価マレイ
ミド化合物がある。ポリマレイミドは多くの場合、ポリ
アミンを合成した後、無水マレイン酸を縮合，脱水反応
させて得られる。従って、高分子量のポリアミンの側鎖
にマレイミド基を導入した時、その導入が不均一になる
おそれがある。また、これらイミド基，マレイミド基を
有する化合物は一般に黄色〜褐色に強く着色しており、
製品の外観を悪くする一因となっている。着色の問題は
脂肪族アミンを原料とする脂肪族ポリイミド，ポリマレ
イミドを用いることによって改善されるが、この方法で
は耐熱性が低下するという新たな問題を生じる。2. Description of the Related Art Conventionally, polyimide has been known as a resin having excellent heat resistance. However, since polyimide itself has poor solubility and meltability, its range of use is limited. As an alternative heat-resistant material, High Polymer Papers Vol. 37, No. 4, 199
Pp. 206, JP-A-61-145225, JP-A-2-21251
There are various polymaleimides described in No. 2 and many polyvalent maleimide compounds. In many cases, polymaleimide is obtained by synthesizing polyamine and then condensing and dehydrating maleic anhydride. Therefore, when a maleimide group is introduced into the side chain of a high molecular weight polyamine, the introduction may be uneven. In addition, these imide groups, compounds having a maleimide group are generally strongly colored yellow to brown,
This is one of the factors that make the appearance of the product worse. Although the coloring problem can be improved by using an aliphatic polyimide or polymaleimide prepared from an aliphatic amine as a raw material, this method causes a new problem that the heat resistance is lowered.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、前述
のイミド系化合物の問題点を解決し、透明性を改善した
耐熱性樹脂を与える多官能モノマ及びその重合体を提供
することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of imide compounds and to provide a polyfunctional monomer and a polymer thereof which give a heat resistant resin with improved transparency. .
【０００４】[0004]
【課題を解決するための手段】本発明を概説すれば以下
の通りである。The outline of the present invention is as follows.
【０００５】化１で表される多官能モノマPolyfunctional monomer represented by Chemical formula 1
【０００６】[0006]
【化７】 [Chemical 7]
【０００７】（但し、Ｒ1 は炭素、炭素二重結合を一つ
有する炭素数４〜５の有機残基であり、Ｒ2 はビニル基
またはビニレン基を有する有機残基を表す）前記化１の
Ｒ1 が(Wherein R 1 is an organic residue having 4 to 5 carbon atoms having one carbon or carbon double bond, and R 2 is an organic residue having a vinyl group or a vinylene group). R 1 of
【０００８】[0008]
【化８】 [Chemical 8]
【０００９】である多官能モノマ。Is a multifunctional monomer.
【００１０】化９で表される多官能モノマ。A polyfunctional monomer represented by Chemical formula 9.
【００１１】[0011]
【化９】 [Chemical 9]
【００１２】（但し、Ｒ1は(However, R 1 is
【００１３】[0013]
【化１０】 [Chemical 10]
【００１４】であり、Ｒ3はAnd R 3 is
【００１５】[0015]
【化１１】 [Chemical 11]
【００１６】であり、Ｒ4はＨ、ＣＨ3を表す） 前述の多官能モノマは置換基としてビニル基，ビニレン
基を有するアミン類と５−ノルボルネン−２，３−ジカ
ルボン酸無水物、cis −１，２，３，６−テトラヒドロ
フタリック酸無水物、cis −４（α−メチルシクロヘキ
セン）−１，２−ジカルボン酸無水物との縮合−脱水反
応から容易に得られる。その例としてはWhere R 4 represents H and CH 3 ) The above-mentioned polyfunctional monomers are amines having a vinyl group or a vinylene group as a substituent, 5-norbornene-2,3-dicarboxylic anhydride, cis- It can be easily obtained from a condensation-dehydration reaction with 1,2,3,6-tetrahydrophthalic acid anhydride and cis-4 (α-methylcyclohexene) -1,2-dicarboxylic acid anhydride. As an example
【００１７】[0017]
【化１２】 [Chemical 12]
【００１８】[0018]
【化１３】 [Chemical 13]
【００１９】[0019]
【化１４】 [Chemical 14]
【００２０】等がある。Etc.
【００２１】化１で表される多官能モノマの何れか一つ
の官能基を重合させて得られる重合体Polymer obtained by polymerizing any one functional group of the polyfunctional monomer represented by Chemical formula 1
【００２２】[0022]
【化１５】 [Chemical 15]
【００２３】（但し、Ｒ1 は炭素、炭素二重結合を一つ
有する炭素数４〜５の有機残基であり、Ｒ2はビニル基
またはビニレン基を有する有機残基を表す） 前述の多官能モノマは種々の重合性モノマとの共重合が
可能であり、その例としては(However, R 1 is an organic residue having 4 to 5 carbon atoms having one carbon or carbon double bond, and R 2 is an organic residue having a vinyl group or a vinylene group.) Functional monomers can be copolymerized with various polymerizable monomers, examples of which are:
【００２４】[0024]
【化１６】 [Chemical 16]
【００２５】（但し、Ｒ5はＨ，ＣＯＯＨ，ＣＯＯＣＨ3
等を表す。）等がある。(However, R 5 is H, COOH, COOCH 3
Etc. ) Etc.
【００２６】[0026]
【作用】本発明の第一の特徴は同一分子内に異なる反応
性を有するビニル基及びビニレン基を有する多官能モノ
マにある。本発明の多官能モノマは加熱により溶融し、
次いで流動性を有するリニアポリマが形成した後、不溶
性の硬化物となるので成形材料に適する。又、置換基の
反応性の違いを利用してThe first feature of the present invention is a polyfunctional monomer having vinyl groups and vinylene groups having different reactivities in the same molecule. The polyfunctional monomer of the present invention is melted by heating,
Then, a linear polymer having fluidity is formed and then becomes an insoluble cured product, which is suitable as a molding material. Also, by utilizing the difference in the reactivity of the substituents
【００２７】[0027]
【化１７】 [Chemical 17]
【００２８】の多官能モノマからはマクロモラキュラス
（Macromolecules １９９１，２４，４４９５−４５０
２ペ−ジ）記載のように、From the polyfunctional monomer (1), macromolecules (Macromolecules 1991, 24, 4495-450)
2 page)
【００２９】[0029]
【化１８】 [Chemical 18]
【００３０】（但し、Ｍはモリブデン，タングステンを
表す。）で表されるカルベン型の開始剤等により、ノル
ボルネン環のみが開環重合した側鎖にビニル基又はビニ
レン基を有する反応性のリニアポリマを得ることがで
き、例えば、アゾビスイソブチルニトリル等のラジカル
重合開始剤によりノルボルネン環以外のビニル基又はビ
ニレン基のみが重合した側鎖にノルボルネン環を有する
反応性のポリマも得ることができる。尚、(Wherein M represents molybdenum and tungsten), a reactive linear polymer having a vinyl group or a vinylene group in the side chain, which is obtained by ring-opening polymerization of only the norbornene ring by a carbene type initiator represented by For example, it is possible to obtain a reactive polymer having a norbornene ring in its side chain obtained by polymerizing only a vinyl group or a vinylene group other than the norbornene ring with a radical polymerization initiator such as azobisisobutylnitrile. still,
【００３１】[0031]
【化１９】 [Chemical 19]
【００３２】[0032]
【化２０】 [Chemical 20]
【００３３】の多官能モノマもアゾビスイソブチルニト
リル等のラジカル重合開始剤により同様のリニアポリマ
を得ることができる。本法によればポリマの繰返し単位
ごとに反応性の置換基を有するポリマが容易に得られ
る。このようにして得られたポリマは加熱等によって架
橋が進行し、架橋密度の高い硬化物を与える。特に多官
能モノマが分子内に芳香環を有している場合は従来のイ
ミド系材料と同等の耐熱性を有する硬化物を与える。
又、多官能モノマは以下に示す構造から明らかなように
イミド環の共役が断ちきられているので、従来のイミド
系材料に比べてその吸光度が極端に小さく、透明性のよ
い硬化物が得られる。With respect to the polyfunctional monomer (1), a similar linear polymer can be obtained by using a radical polymerization initiator such as azobisisobutylnitrile. According to this method, a polymer having a reactive substituent for each repeating unit of the polymer can be easily obtained. The polymer thus obtained undergoes crosslinking due to heating or the like to give a cured product having a high crosslinking density. In particular, when the polyfunctional monomer has an aromatic ring in the molecule, it gives a cured product having heat resistance equivalent to that of a conventional imide material.
Further, since the imide ring conjugation is cut off in the polyfunctional monomer as is clear from the structure shown below, its absorbance is extremely small compared to conventional imide-based materials, and a cured product with good transparency is obtained. To be
【００３４】[0034]
【化２１】 [Chemical 21]
【００３５】（但し、Ｒ1 は炭素、炭素二重結合を一つ
有する炭素数４〜５の有機残基であり、Ｒ2 はビニル基
またはビニレン基を有する有機残基を表す） 更に該多官能モノマは各種のノルボルネン環を有する化
合物、又はアクリル酸（エステル），メタクリル酸（エ
ステル），スチレン，スチレン誘導体等のラジカル重合
可能な種々のモノマとの共重合が容易である。(Wherein R 1 is an organic residue having 4 to 5 carbon atoms having one carbon or carbon double bond, and R 2 is an organic residue having a vinyl group or a vinylene group). The functional monomer can be easily copolymerized with various norbornene ring-containing compounds or various radically polymerizable monomers such as acrylic acid (ester), methacrylic acid (ester), styrene, and styrene derivatives.
【００３６】[0036]
【実施例】以下に本発明の実施例を示す。EXAMPLES Examples of the present invention will be shown below.
【００３７】（比較例）無水マレイン酸（４２.２ｇ ）
のジエチルエーテル（１５００cc）溶液にｐ−アミノス
チレン（５１.４ｇ ）のジエチルエーテル（５００cc）
溶液を撹拌しながら１時間かけて滴下し、更に２時間撹
拌をつづけた。沈殿物を濾別，洗浄，乾燥して前駆体を
得た（収率９８モル％）。前駆体（１０.９ｇ ），無水
酢酸（１５０.０ｇ），無水酢酸ナトリウム（１９.０
ｇ）の混合物を１００℃で２時間加熱した。反応溶液を
多量の氷水に注ぎ、沈殿物を濾別，洗浄した後、ジエチ
ルエーテルで抽出してＮ−（４−ビニルフェニル）マレ
イミドを得た（収率４０モル％）。(Comparative Example) Maleic anhydride (42.2 g)
Solution of p-aminostyrene (51.4 g) in diethyl ether (500 cc).
The solution was added dropwise with stirring over 1 hour, and stirring was continued for another 2 hours. The precipitate was separated by filtration, washed and dried to obtain a precursor (yield 98 mol%). Precursor (10.9g), acetic anhydride (150.0g), anhydrous sodium acetate (19.0g)
The mixture of g) was heated at 100 ° C. for 2 hours. The reaction solution was poured into a large amount of ice water, the precipitate was separated by filtration, washed and then extracted with diethyl ether to obtain N- (4-vinylphenyl) maleimide (yield 40 mol%).
【００３８】日立製５５７型二波長分光光度計を用いて
Ｎ−（４−ビニルフェニル）マレイミドの吸光スペクト
ルを観測した。その結果を構造と共に図１に示した。３
６５nmにおけるモル吸光係数は１９６リットル／mol・c
mであった。The absorption spectrum of N- (4-vinylphenyl) maleimide was observed using a Hitachi 557 type dual wavelength spectrophotometer. The results are shown in FIG. 1 together with the structure. Three
Molar extinction coefficient at 65 nm is 196 liters / mol.c
It was m.
【００３９】ａ）デュポン社製９１０型示差走査熱量計
を用いてＮ−（４−ビニルフェニル）マレイミドを空気
中、１０℃／分で加熱し、融点，発熱ピ−クを観測し
た。その結果、１０９℃付近で溶融し、１３０℃付近で
架橋した。A) N- (4-vinylphenyl) maleimide was heated in air at 10 ° C./min using a DuPont Model 910 differential scanning calorimeter, and the melting point and exothermic peak were observed. As a result, it melted at around 109 ° C and crosslinked at around 130 ° C.
【００４０】ｂ）真空理工製高速示差熱天秤を用いて
（４−ビニルフェニル）マレイミドを窒素気流下５℃／
分で加熱し、５％重量減少する温度を熱分解温度として
調べた。その結果、熱分解温度は４６０℃であった。B) Using a high-speed differential thermal balance manufactured by Vacuum Riko Co., Ltd., (4-vinylphenyl) maleimide was added at 5 ° C. under a nitrogen stream.
It was heated in minutes and the temperature at which the weight was reduced by 5% was examined as the thermal decomposition temperature. As a result, the thermal decomposition temperature was 460 ° C.
【００４１】（実施例１）５−ノルボルネン−２，３−
ジカルボン酸無水物（７０.６ｇ ）のジエチルエーテル
（１５００cc）溶液にｐ−アミノスチレン（５１.４ｇ
）のジエチルエーテル（５００cc）溶液を撹拌しなが
ら１時間かけて滴下し、更に２時間撹拌をつづけた。沈
殿物を濾別，洗浄，乾燥して前駆体１を得た（収率９８
モル％）。前駆体１（１３.３ｇ），無水酢酸(１５０.
０ｇ)，無水酢酸ナトリウム（１９.０ｇ）の混合物を１
００℃で２時間加熱した。反応溶液を多量の氷水に注
ぎ、沈殿物を濾別，洗浄した後、ジエチルエーテルで抽
出してＮ−(４−ビニルフェニル)ハイミックイミドを得
た（収率４０モル％）。(Example 1) 5-norbornene-2,3-
A solution of dicarboxylic acid anhydride (70.6 g) in diethyl ether (1500 cc) was added with p-aminostyrene (51.4 g).
A solution of)) in diethyl ether (500 cc) was added dropwise with stirring over 1 hour, and stirring was continued for another 2 hours. The precipitate was filtered off, washed and dried to obtain a precursor 1 (yield 98
Mol%). Precursor 1 (13.3 g), acetic anhydride (150.
0 g) and anhydrous sodium acetate (19.0 g) as a mixture of 1
Heated at 00 ° C. for 2 hours. The reaction solution was poured into a large amount of ice water, the precipitate was separated by filtration, washed, and then extracted with diethyl ether to obtain N- (4-vinylphenyl) hymic imide (yield 40 mol%).
【００４２】比較例と同様にしてＮ−（４−ビニルフェ
ニル）ハイミックイミドの吸光スペクトルを観測した。
その結果を構造と共に図１に併記した。３６５nmにおけ
るモル吸光係数は２リットル／mol・cmであった。The absorption spectrum of N- (4-vinylphenyl) hymic imide was observed in the same manner as in Comparative Example.
The results are shown together with the structure in FIG. The molar extinction coefficient at 365 nm was 2 liter / mol · cm.
【００４３】ａ）比較例と同様にして融点，発熱ピーク
を観測した。その結果、１４０℃付近で溶融し、１６０
℃付近で架橋した。A) Melting point and exothermic peak were observed in the same manner as in Comparative Example. As a result, it melts at around 140 ° C,
Crosslinked at around ℃.
【００４４】ｂ）比較例と同様にして熱分解温度を調べ
た。その結果、熱分解温度は４６０℃であった。B) The thermal decomposition temperature was examined in the same manner as in the comparative example. As a result, the thermal decomposition temperature was 460 ° C.
【００４５】（実施例２）cis−１，２，３，６−テト
ラヒドロフタリック酸無水物（７０.６ｇ）のジエチル
エーテル（１５００cc）溶液にｐ−アミノスチレン（５
１.４ｇ ）のジエチルエーテル（５００cc）溶液を撹拌
しながら１時間かけて滴下し、更に２時間撹拌をつづけ
た。沈殿物を濾別，洗浄，乾燥して前駆体２を得た(収
率９８モル％)。前駆体２（１２.７ｇ），無水酢酸（１
５０.０ｇ），無水酢酸ナトリウム（１９.０ｇ ）の混
合物を１００℃で２時間加熱した。反応溶液を多量の氷
水に注ぎ、沈殿物を濾別，洗浄した後、ジエチルエーテ
ルで抽出してＮ−（４−ビニルフェニル）−Δ−ｃｉｓ
−テトラヒドロフタリックイミドを得た（収率４０モル
％）。Example 2 A solution of cis-1,2,3,6-tetrahydrophthalic anhydride (70.6 g) in diethyl ether (1500 cc) was added to p-aminostyrene (5
A solution of 1.4 g) in diethyl ether (500 cc) was added dropwise with stirring over 1 hour, and stirring was continued for another 2 hours. The precipitate was filtered off, washed and dried to obtain precursor 2 (yield 98 mol%). Precursor 2 (12.7 g), acetic anhydride (1
A mixture of 50.0 g) and anhydrous sodium acetate (19.0 g) was heated at 100 ° C for 2 hours. The reaction solution was poured into a large amount of ice water, the precipitate was separated by filtration, washed, and then extracted with diethyl ether to obtain N- (4-vinylphenyl) -Δ-cis.
-Tetrahydrophthalic imide was obtained (yield 40 mol%).
【００４６】比較例と同様にしてＮ−（４−ビニルフェ
ニル）−Δ−cis −テトラヒドロフタリックイミドの吸
光スペクトルを観測した。その結果を構造と共に図１に
併記した。３６５nmにおけるモル吸光係数は２リットル
／mol・cmであった。The absorption spectrum of N- (4-vinylphenyl) -Δ-cis-tetrahydrophthalic imide was observed in the same manner as in Comparative Example. The results are shown together with the structure in FIG. The molar extinction coefficient at 365 nm was 2 liter / mol · cm.
【００４７】ａ）比較例と同様にして融点，発熱ピーク
を観測した。その結果、８２℃付近で溶融し、１０２℃
付近で架橋した。A) Melting point and exothermic peak were observed in the same manner as in Comparative Example. As a result, it melts at around 82 ℃,
Crosslinked in the vicinity.
【００４８】ｂ）比較例と同様にして熱分解温度を調べ
た。その結果、熱分解温度は４１０℃であった。B) The thermal decomposition temperature was examined in the same manner as in the comparative example. As a result, the thermal decomposition temperature was 410 ° C.
【００４９】（実施例３）Ｎ−（４−ビニルフェニル）
ハイミックイミド（２.６５ｇ ），アゾビスイソブチル
ニトリル（０.０６ｇ ）を４０ccのトルエンに溶解し、
８６℃に加熱した。１０時間加熱を続けた後、多量のメ
タノールに反応溶液を注ぎ沈殿物を得た（収率６０
％）。得られたポリマはジクロロメタン，ジメチルスル
ホキシドに可溶であった。1Ｈ−ＮＭＲ の観測結果を図
２に示した。(Example 3) N- (4-vinylphenyl)
Hymic imide (2.65 g) and azobisisobutylnitrile (0.06 g) were dissolved in 40 cc of toluene,
Heated to 86 ° C. After continuing heating for 10 hours, the reaction solution was poured into a large amount of methanol to obtain a precipitate (yield 60
%). The obtained polymer was soluble in dichloromethane and dimethyl sulfoxide. The result of 1 H-NMR observation is shown in FIG.
【００５０】（実施例４）Ｎ−（４−ビニルフェニル）
−Δ−ｃｉｓ−テトラヒドロフタリックイミド（２.５
３ｇ），アゾビスイソブチルニトリル（０.０６ｇ）を
４０ccのトルエンに溶解し、８６℃に加熱した。１０時
間加熱を続けた後、多量のメタノ−ルに反応溶液を注ぎ
沈殿物を得た（収率６０％）。得られたポリマはジクロ
ロメタン，ジメチルスルホキシドに可溶であった。(Example 4) N- (4-vinylphenyl)
-Δ-cis-tetrahydrophthalic imide (2.5
3 g) and azobisisobutylnitrile (0.06 g) were dissolved in 40 cc of toluene and heated to 86 ° C. After continuing heating for 10 hours, the reaction solution was poured into a large amount of methanol to obtain a precipitate (yield 60%). The obtained polymer was soluble in dichloromethane and dimethyl sulfoxide.
【００５１】（実施例５）窒素気流下、Ｎ−（４−ビニ
ルフェニル）ハイミックイミド（２.６５ｇ ）、Example 5 Under a nitrogen stream, N- (4-vinylphenyl) hymic imide (2.65 g),
【００５２】[0052]
【化２２】 [Chemical formula 22]
【００５３】のカルベン錯体（０.０８ｇ ）を４０ccの
トルエンに溶解し、８６℃に加熱した。１０時間加熱を
続けた後、多量のメタノールに反応溶液を注ぎ沈殿物を
得た（収率７０％）。得られたポリマはジクロロメタ
ン，ジメチルスルホキシドに可溶であった。The carbene complex of (0.08 g) was dissolved in 40 cc of toluene and heated to 86 ° C. After continuing heating for 10 hours, the reaction solution was poured into a large amount of methanol to obtain a precipitate (yield 70%). The obtained polymer was soluble in dichloromethane and dimethyl sulfoxide.
【００５４】（実施例６）Ｎ−（４−ビニルフェニル）
ハイミックイミド(２.６５ｇ)，スチレン（２.０ｇ），
アゾビスイソブチルニトリル（０.１８ｇ ）を８０ccの
トルエンに溶解し、８６℃に加熱した。１０時間加熱を
続けた後、多量のメタノールに反応溶液を注ぎ沈殿物を
得た（収率６０％）。得られたポリマはジクロロメタ
ン，ジメチルスルホキシドに可溶であった。(Example 6) N- (4-vinylphenyl)
Hymic imide (2.65g), styrene (2.0g),
Azobisisobutyl nitrile (0.18 g) was dissolved in 80 cc of toluene and heated to 86 ° C. After continuing heating for 10 hours, the reaction solution was poured into a large amount of methanol to obtain a precipitate (yield 60%). The obtained polymer was soluble in dichloromethane and dimethyl sulfoxide.
【００５５】（実施例７）Ｎ−（４−ビニルフェニル）
−Δ−ｃｉｓ−テトラヒドロフタリックイミド（２.５
３ｇ），スチレン（２.０ｇ），アゾビスイソブチルニ
トリル（０.１８ｇ）を８０ccのトルエンに溶解し、８
６℃に加熱した。１０時間加熱を続けた後、多量のメタ
ノールに反応溶液を注ぎ沈殿物を得た（収率６０％）。
得られたポリマはジクロロメタン，ジメチルスルホキシ
ドに可溶であった。(Example 7) N- (4-vinylphenyl)
-Δ-cis-tetrahydrophthalic imide (2.5
3 g), styrene (2.0 g) and azobisisobutyl nitrile (0.18 g) were dissolved in 80 cc of toluene,
Heated to 6 ° C. After continuing heating for 10 hours, the reaction solution was poured into a large amount of methanol to obtain a precipitate (yield 60%).
The obtained polymer was soluble in dichloromethane and dimethyl sulfoxide.
【００５６】[0056]
【発明の効果】本発明は従来のイミド系材料と同等の耐
熱性を有し、透明性に優れた多官能モノマ及び重合体を
得た。INDUSTRIAL APPLICABILITY According to the present invention, a polyfunctional monomer and a polymer having heat resistance equivalent to that of a conventional imide material and excellent transparency are obtained.
【図１】本発明の多官能モノマの吸光スペクトルの説明
図。FIG. 1 is an explanatory diagram of an absorption spectrum of a polyfunctional monomer of the present invention.
【図２】本発明の多官能モノマ及びラジカル重合体の1
Ｈ−ＮＭＲ スペクトル例の説明図。FIG. 2 is one of the polyfunctional monomers and radical polymers of the present invention.
Explanatory drawing of the example of a H-NMR spectrum.
１…Ｎ−（４−ビニルフェニル）マレイミド、２…Ｎ−
(４−ビニルフェニル)ハイミックイミド、３…Ｎ−（４
−ビニルフェニル）−Δ−cis −フタリックイミド。1 ... N- (4-vinylphenyl) maleimide, 2 ... N-
(4-Vinylphenyl) hymic imide, 3 ... N- (4
-Vinylphenyl) -Δ-cis-phthalic imide.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 昭雄 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 坂田 純一 広島県福山市郷分町950番地の１ マナッ ク株式会社内 (72)発明者 河内 博美 広島県福山市郷分町950番地の１ マナッ ク株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Takahashi 7-1-1 Omika-cho, Hitachi-shi, Ibaraki Hitachi Ltd. Hitachi Research Laboratory (72) Inventor Junichi Sakata 950 Gobuncho, Fukuyama-shi, Hiroshima No. 1 Manac Co., Ltd. (72) Inventor Hiromi Kawachi No. 1 Manac Co., Ltd. at 950 Gobuncho, Fukuyama City, Hiroshima Prefecture
Claims (4)
４〜５の有機残基であり、Ｒ2はビニル基またはビニレ
ン基を有する有機残基を表す）1. A polyfunctional monomer represented by Chemical formula 1. [Chemical 1] (However, R 1 is an organic residue having 4 to 5 carbon atoms having one carbon or carbon double bond, and R 2 is an organic residue having a vinyl group or a vinylene group.)
モノマ。 【化３】 （但し、Ｒ1は 【化４】 であり、Ｒ3は 【化５】 であり、Ｒ4はＨ，ＣＨ3を表す）3. The polyfunctional monomer represented by Chemical formula 3 in claim 2. [Chemical 3] (However, R 1 is And R 3 is And R 4 represents H, CH 3 )
モノマの何れか一つの官能基を重合させて得られる重合
体を含有する樹脂組成物。 【化６】 （但し、Ｒ1 は炭素、炭素二重結合を一つ有する炭素数
４〜５の有機残基であり、Ｒ2はビニル基またはビニレ
ン基を有する有機残基を表す）4. A resin composition containing a polymer obtained by polymerizing any one of the functional groups of the polyfunctional monomer represented by Chemical Formula 1 in claim 1. [Chemical 6] (However, R 1 is an organic residue having 4 to 5 carbon atoms having one carbon or carbon double bond, and R 2 is an organic residue having a vinyl group or a vinylene group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6001485A JPH07206934A (en) | 1994-01-12 | 1994-01-12 | Polyfunctional monomer and its polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6001485A JPH07206934A (en) | 1994-01-12 | 1994-01-12 | Polyfunctional monomer and its polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07206934A true JPH07206934A (en) | 1995-08-08 |
Family
ID=11502751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6001485A Pending JPH07206934A (en) | 1994-01-12 | 1994-01-12 | Polyfunctional monomer and its polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07206934A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61156145A (en) * | 1984-12-28 | 1986-07-15 | Hitachi Chem Co Ltd | Electrostatic charge image developing toner |
| JPS63317530A (en) * | 1987-05-22 | 1988-12-26 | チバーガイギー アクチエンゲゼルシヤフト | Bisimides and composition containing them |
| JPS6454459A (en) * | 1987-08-25 | 1989-03-01 | Hitachi Chemical Co Ltd | Electrostatic charge image developing toner |
| JPH02100054A (en) * | 1988-10-07 | 1990-04-12 | Fuji Photo Film Co Ltd | Positive type photosensitive composition |
-
1994
- 1994-01-12 JP JP6001485A patent/JPH07206934A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61156145A (en) * | 1984-12-28 | 1986-07-15 | Hitachi Chem Co Ltd | Electrostatic charge image developing toner |
| JPS63317530A (en) * | 1987-05-22 | 1988-12-26 | チバーガイギー アクチエンゲゼルシヤフト | Bisimides and composition containing them |
| JPS6454459A (en) * | 1987-08-25 | 1989-03-01 | Hitachi Chemical Co Ltd | Electrostatic charge image developing toner |
| JPH02100054A (en) * | 1988-10-07 | 1990-04-12 | Fuji Photo Film Co Ltd | Positive type photosensitive composition |
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