JPH05140305A - Fluorine-containing biscyamide resin composition - Google Patents
Fluorine-containing biscyamide resin compositionInfo
- Publication number
- JPH05140305A JPH05140305A JP30151791A JP30151791A JPH05140305A JP H05140305 A JPH05140305 A JP H05140305A JP 30151791 A JP30151791 A JP 30151791A JP 30151791 A JP30151791 A JP 30151791A JP H05140305 A JPH05140305 A JP H05140305A
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- Prior art keywords
- resin composition
- compound
- group
- formula
- polymerization
- 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.)
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- Organic Insulating Materials (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は含フッ素熱硬化性樹脂組
成物に係り、特に、成形性,耐熱性及び、接着性に優れ
た低誘電率絶縁材料として好適な樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing thermosetting resin composition, and more particularly to a resin composition suitable as a low dielectric constant insulating material excellent in moldability, heat resistance and adhesiveness.
【0002】[0002]
【従来の技術】耐熱性の熱硬化性樹脂組成物として従来
ビスマレイミド等が用いられてきたがビスマレイミドに
ビスシアナミドを加えた組成物による樹脂は耐熱性,成
形性が改善されることが見出されている(特開昭58−71
924号公報)。しかし、これらの樹脂は分極率の大きい
アミド基やイミド基を多数もつために比誘電率が比較的
高いことが知られている。比誘電率の低い熱硬化性樹脂
組成物としては含フッ素マレイミド等を用いた樹脂が提
案されているが(特開平2−73809号公報)フッ素を導入
したことにより接着性が低下することが知られている。
そのため、信号の高速伝送の要求される大型計算機の多
層プリント板に使用するためには接着性と比誘電率の低
さを兼ね備えた材料が要求されている。2. Description of the Related Art Bismaleimide has been conventionally used as a heat-resistant thermosetting resin composition, but it has been found that a resin obtained by adding bismaleamide to bismaleimide has improved heat resistance and moldability. Issued (JP-A-58-71)
No. 924 publication). However, it is known that these resins have a relatively high relative dielectric constant because they have a large number of amide groups or imide groups having a large polarizability. As a thermosetting resin composition having a low relative dielectric constant, a resin using a fluorine-containing maleimide or the like has been proposed (JP-A-2-73809), but it is known that the introduction of fluorine reduces the adhesiveness. Has been.
Therefore, a material having both adhesiveness and low relative permittivity is required for use in a multilayer printed board of a large-sized computer that requires high-speed signal transmission.
【0003】[0003]
【発明が解決しようとする課題】従来の熱硬化性樹脂の
組成物は比誘電率を低下させる手段としてフッ素置換し
た官能基を導入していたが、この方法には金属との接着
性が損なわれるという欠点がある。一般に、接着性を改
善するためにはエステル等の極性をもつ官能基を導入す
れば良いことが知られているが、通常の方法では比誘電
率が高くなる。In the conventional thermosetting resin composition, a fluorine-substituted functional group was introduced as a means for lowering the relative dielectric constant, but this method impairs the adhesiveness to a metal. There is a drawback that In general, it is known that a polar functional group such as an ester may be introduced to improve the adhesiveness, but in a usual method, the relative dielectric constant becomes high.
【0004】本発明の目的は耐熱性,接着性を損なうこ
となしに比誘電率が低く、さらに、イミド系材料の特徴
である成形時の副生成物を発生しない樹脂組成物を提供
することにある。An object of the present invention is to provide a resin composition which has a low relative dielectric constant without impairing heat resistance and adhesiveness and does not generate a by-product during molding which is a characteristic of imide-based materials. is there.
【0005】[0005]
【課題を解決するための手段】本発明を概説すれば、極
性をもつ官能基と共に、その導入による比誘電率の上昇
を補えるような含フッ素マレイミド化合物と含フッ素シ
アナミド化合物を組み合わせることにより耐熱性,接着
性を損なうことなしに比誘電率が低く、さらに、イミド
系材料の特徴である成形時の副生成物を発生しない樹脂
組成物を提供することができる。The present invention will be described in brief. By combining a functional group having a polarity with a fluorine-containing maleimide compound and a fluorine-containing cyanamide compound that can compensate for an increase in the relative dielectric constant due to the introduction thereof, heat resistance can be improved. It is possible to provide a resin composition which has a low relative dielectric constant without impairing adhesiveness and does not generate a by-product at the time of molding, which is a feature of imide-based materials.
【0006】請求項1 一般式(1)Claim 1 General formula (1)
【0007】[0007]
【化11】 [Chemical 11]
【0008】(式中、Rは水素,アルキル基、あるいは
ハロゲン、nは1〜4の整数を示す。)で表されるビス
マレイミド化合物と、一般式(2)(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)
【0009】[0009]
【化12】 [Chemical 12]
【0010】(式中、C9F17 基は二重結合を一個もつ
パーフルオロノネニル基を、Xはエステル結合、あるい
はエーテル結合を含む2価の基を示す。)で表されるビ
スシアナミド化合物を含むことを特徴とする熱硬化性樹
脂組成物。(Wherein, C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A thermosetting resin composition comprising a compound.
【0011】請求項2 請求項1のビスマレイミド化合
物と請求項1のビスシアナミド化合物を混合比95:5
〜5:95で用いることを特徴とする熱硬化性樹脂組成
物。 請求項3 一般式(1)(2) A mixing ratio of the bismaleimide compound of (1) and the biscyanamide compound of (1) is 95: 5.
A thermosetting resin composition, characterized in that it is used at 5:95. Claim 3 General formula (1)
【0012】[0012]
【化13】 [Chemical 13]
【0013】(式中、Rは水素,アルキル基、あるいは
ハロゲン、nは1〜4の整数を示す。)で表されるビス
マレイミド化合物と、一般式(2)(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)
【0014】[0014]
【化14】 [Chemical 14]
【0015】(式中、C9F17 基は二重結合を一個をも
つパーフルオロノネニル基を、Xはエステル結合、ある
いはエーテル結合を含む2価の基を示す。)で表される
ビスシアナミド化合物及び、マレイミド化合物,シアナ
ミド化合物,シアナト化合物,イソシアナト化合物,エ
ポキシ化合物,ビニル化合物の中の少なくとも一種類を
含むことを特徴とする熱硬化性樹脂組成物。(In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A thermosetting resin composition comprising a cyanamide compound and at least one of a maleimide compound, a cyanamide compound, a cyanato compound, an isocyanato compound, an epoxy compound and a vinyl compound.
【0016】請求項4 請求項1,2または3において
樹脂組成物を溶媒に溶解し、均一なワニスにより作製す
る樹脂組成物。4. A resin composition prepared by dissolving the resin composition in a solvent according to claim 1, 2 or 3 and using a uniform varnish.
【0017】請求項5 一般式(1)Claim 5 General formula (1)
【0018】[0018]
【化15】 [Chemical 15]
【0019】(式中、Rは水素,アルキル基、あるいは
ハロゲン、nは1〜4の整数を示す。)で表されるビス
マレイミド化合物と、一般式(2)(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)
【0020】[0020]
【化16】 [Chemical 16]
【0021】(式中、C9F17 基は二重結合を一個もつ
パーフルオロノネニル基を、Xはエステル結合、あるい
はエーテル結合を含む2価の基を示す。)で表されるビ
スシアナミド化合物を用いて多重結合の重合反応により
三次元架橋硬化物を得ることを特徴とする樹脂硬化物の
製造方法。(Wherein C 9 F 17 is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A method for producing a cured resin product, which comprises using a compound to obtain a three-dimensional crosslinked cured product by a polymerization reaction of multiple bonds.
【0022】請求項6 請求項5において多重結合の重
合反応が加熱重合であることを特徴とする樹脂硬化物の
製造方法。6. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is heat polymerization.
【0023】請求項7 請求項5において多重結合の重
合反応がアルコキシ化合物等のアニオン重合開始剤の存
在下での重合である樹脂硬化物の製造方法。7. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.
【0024】請求項8 請求項5において多重結合の重
合反応が過酸化物等のラジカル重合開始剤の存在下での
重合である樹脂硬化物の製造方法。8. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide.
【0025】請求項9 請求項5において多重結合の重
合反応がUV照射等の光重合である樹脂硬化物の製造方
法。9. A method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.
【0026】請求項10 一般式(1)Claim 10 General formula (1)
【0027】[0027]
【化17】 [Chemical 17]
【0028】(式中、Rは水素,アルキル基、あるいは
ハロゲン、nは1〜4の整数を示す。)で表されるビス
マレイミド化合物と、一般式(2)(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)
【0029】[0029]
【化18】 [Chemical 18]
【0030】(式中、C9F17 基は二重結合を一個もつ
パーフルオロノネニル基を、Xはエステル結合、あるい
はエーテル結合を含む2価の基を示す。)で表されるビ
スシアナミド化合物を含む樹脂組成物を多重結合の重合
反応により三次元架橋して得られる硬化物。(Wherein, C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). A cured product obtained by three-dimensionally crosslinking a resin composition containing a compound by a polymerization reaction of multiple bonds.
【0031】請求項11 請求項10において多重結合
の重合反応が加熱重合である樹脂硬化物。11. A cured resin product according to claim 10, wherein the polymerization reaction of the multiple bonds is heat polymerization.
【0032】請求項12 請求項10において多重結合
の重合反応がアルコキシ化合物等のアニオン重合開始剤
の存在下での重合である樹脂硬化物。12. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.
【0033】請求項13 請求項10において多重結合
の重合反応が過酸化物等のラジカル重合開始剤の存在下
での重合である樹脂硬化物。13. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide.
【0034】請求項14 請求項10において多重結合
の重合反応がUV照射等の光重合である樹脂硬化物。14. A cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.
【0035】請求項15 請求項10において硬化物の
比誘電率が3以下である硬化物。15. A cured product according to claim 10, which has a relative dielectric constant of 3 or less.
【0036】請求項16 一般式(1)Claim 16 General formula (1)
【0037】[0037]
【化19】 [Chemical 19]
【0038】(式中、Rは水素,アルキル基、あるいは
ハロゲン、nは1〜4の整数を示す。)で表されるビス
マレイミド化合物と、一般式(2)(Wherein R represents hydrogen, an alkyl group, or halogen, and n represents an integer of 1 to 4), and a bismaleimide compound represented by the general formula (2)
【0039】[0039]
【化20】 [Chemical 20]
【0040】(式中、C9F17 基は二重結合を一個もつ
パーフルオロノネニル基を、Xはエステル結合、あるい
はエーテル結合を含む2価の基を示す。)で表されるビ
スシアナミド化合物を含む樹脂組成物を、多重結合の重
合反応により三次元架橋して得られる硬化物を用いた電
気絶縁体。(Wherein, C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond). An electrical insulator using a cured product obtained by three-dimensionally crosslinking a resin composition containing a compound by a polymerization reaction of multiple bonds.
【0041】請求項17 請求項1,2,3または4に
記載の樹脂組成物を補強材である無機繊維布に含浸させ
て得られるプリプレグ。(17) A prepreg obtained by impregnating an inorganic fiber cloth, which is a reinforcing material, with the resin composition according to (1), (2), (3) or (4).
【0042】請求項18 請求項1,2,3または4に
記載の樹脂組成物を補強材である有機繊維布に含浸させ
て得られるプリプレグ。18. A prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
【0043】請求項19 請求項1,2,3または4に
記載の樹脂組成物を用いた積層材料。(19) A laminated material using the resin composition according to (1), (2), (3) or (4).
【0044】請求項20 請求項1,2,3または4に
記載の樹脂組成物を他の樹脂成分と共に用いた積層材
料。20. A laminate material using the resin composition according to claim 1, 2, 3 or 4 together with other resin components.
【0045】請求項21 請求項1,2,3または4に
記載の樹脂組成物を補強材である無機繊維布に含浸させ
て得られるプリプレグを積層接着して得られる積層材
料。21. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
【0046】請求項22 請求項1,2,3または4に
記載の樹脂組成物を補強材である有機繊維布に含浸させ
て得られるプリプレグを積層接着して得られる積層材
料。22. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
【0047】請求項23 請求項1ないし22に記載の
樹脂組成物及び該組成物を用いた積層材料により構成さ
れる配線板。[23] A wiring board comprising the resin composition according to any one of [1] to [22] and a laminated material using the composition.
【0048】請求項24 請求項1ないし22に記載の
樹脂組成物及び該組成物を用いた積層材料により構成さ
れる大面積基板。24. A large area substrate comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.
【0049】請求項25 請求項1ないし22に記載の
樹脂組成物及び該組成物を用いた積層材料により構成さ
れるモジュール基板。25. A module substrate comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.
【0050】請求項26 請求項1ないし22に記載の
樹脂組成物及び該組成物を用いた積層材料により構成さ
れるマイクロチップキャリア基板。[26] A microchip carrier substrate comprising the resin composition according to any one of [1] to [22] and a laminated material using the composition.
【0051】請求項27 請求項1ないし22に記載の
樹脂組成物及び該組成物を用いた積層材料により構成さ
れるピングリッドアレイ基板。(27) A pin grid array substrate formed of the resin composition according to any one of (1) to (22) and a laminated material using the composition.
【0052】本発明において前記一般式(1)で表され
る含フッ素マレイミド化合物は、例えば以下に示したも
のがある。In the present invention, examples of the fluorine-containing maleimide compound represented by the general formula (1) are shown below.
【0053】[0053]
【化21】 [Chemical 21]
【0054】また、本発明において前記一般式(2)で
表される含フッ素シアナミド化合物は、例えば以下に示
したものがある。Further, the fluorine-containing cyanamide compound represented by the general formula (2) in the present invention includes, for example, those shown below.
【0055】[0055]
【化22】 [Chemical formula 22]
【0056】ただし、ここでC9F17 基は例えば以下に
示したものがある。However, examples of the C 9 F 17 group include those shown below.
【0057】[0057]
【化23】 [Chemical formula 23]
【0058】これらの化合物は接着性を向上させる極性
基をもつにもかかわらず、水素と比較して炭素との結合
解離エネルギが100kJ/mol 大きく、かつ、モル比
容の大きなフッ素の含有率の高い置換基を合わせ持つの
で接着性,耐熱性にすぐれ、比誘電率の低い熱硬化性樹
脂を得ることが可能となった。Although these compounds have polar groups for improving the adhesiveness, the bond dissociation energy with carbon is 100 kJ / mol greater than that of hydrogen, and the content of fluorine having a large molar specific volume is large. Since it also has high substituents, it has excellent adhesiveness and heat resistance, and it has become possible to obtain thermosetting resins with a low dielectric constant.
【0059】これらの化合物を熱硬化性樹脂の組成物と
して用いることにより樹脂の成形性を向上させることが
でき、同時にフッ素置換された置換基をもっているので
耐熱性にすぐれ、比誘電率の低い樹脂を得ることができ
た。By using these compounds as the composition of thermosetting resin, the moldability of the resin can be improved, and at the same time, since it has a fluorine-substituted substituent, the resin has excellent heat resistance and a low dielectric constant. I was able to get
【0060】含フッ素シアナミド化合物と含フッ素マレ
イミド化合物を用いた熱硬化性樹脂は加熱等の三量化反
応により複素芳香環であるメラミン環やイソメラミン環
とイミド環の形成や複雑な三次元架橋により耐熱性に優
れた低誘電率材料となる。これにより高温でも機械的特
性,寸法安定性等を保持した耐熱性絶縁材料となる。ま
た、この架橋硬化反応で縮合水等の反応副生成物を発生
しないため各種構造材料,モールド成形等の多くの分野
で適用できる利点がある。これは耐熱性絶縁材料として
代表的なポリイミド,ポリベンゾイミダゾール,ポリベ
ンゾチアゾール等と異なる点である。A thermosetting resin using a fluorinated cyanamide compound and a fluorinated maleimide compound is resistant to heat due to the formation of a melamine ring which is a heteroaromatic ring or an isomer ring of an isomeramine ring and a complex three-dimensional cross-linking by a trimerization reaction such as heating. A low dielectric constant material with excellent properties. This results in a heat-resistant insulating material that retains mechanical properties and dimensional stability even at high temperatures. Further, since the reaction by-product such as condensed water is not generated in this crosslinking and curing reaction, there is an advantage that it can be applied in various fields such as various structural materials and molding. This is different from typical heat-resistant insulating materials such as polyimide, polybenzimidazole, and polybenzothiazole.
【0061】[0061]
【作用】熱硬化性樹脂の接着性を向上させるために導入
した極性基による誘電率の上昇は、炭素との結合解離エ
ネルギが水素より100kJ/mol 大きく、かつ、モル
比容の大きなフッ素の含有率の高い置換基を導入するこ
とで可能となった。耐熱性は多重結合の重合反応によっ
て三次元架橋結合を構築するマレイミドとシアナミド構
造を保持することによって従来の特性を維持できた。The polar group introduced to improve the adhesiveness of the thermosetting resin raises the dielectric constant because the bond dissociation energy with carbon is 100 kJ / mol higher than that of hydrogen and the inclusion of fluorine with a large molar specific volume. It became possible by introducing a substituent with a high ratio. The heat resistance was able to maintain the conventional properties by retaining the maleimide and cyanamide structures that construct a three-dimensional cross-link by the polymerization reaction of multiple bonds.
【0062】[0062]
〈実施例1〉2,2−ビス(4−(4−マレイミドフェ
ノキシ)フェニル)−1,1,1,3,3,3−ヘキサ
フルオロプロパン(A)(セントラル硝子)80gと1
−パーフルオロノネニルオキシ−3,5−フタロイルビ
ス(4−(4−シアナミドフェノキシ)フェニル)
(C)(マナック)20gをメチルイソブチルケトン10
0gに溶かし、100℃,60分還流下でプレポリマ化
を行った。室温まで冷却後真空乾燥により溶媒を除去し
粉末状の試料を得た。得られた試料を厚さ2mmのスペー
サを用いてプレス成形により硬化物の樹脂板を得た。硬
化条件は150℃で試料を、一旦、溶融した後、250
℃に昇温し加圧した。得られた樹脂板について特性評価
した。比誘電率は、ヒューレット パッカード社製LF
インピーダンスアナライザ4192Aを用い、JIS−
C−6481に従い試料の静電容量を測定し比誘電率を
計算した。熱膨張率に関しては、真空理工製熱機械特性
測定装置TM−3000を用い、樹脂板から7mm×7mm
に切り出した試料の厚さ方向の熱膨張率(50〜220
℃)測定した。昇温速度2℃/min ,荷重10gの圧縮
モードで測定した。曲げ強度は島津製作所製オートグラ
フDDS−5000を用い、JIS−C−6481に従
い測定した。樹脂板から50mm×5mmに切り出した試料
について支点間距離30mm,たわみ速度2mm/min の条
件で測定した。熱分解開始温度については、真空理工製
高速示差熱天秤TGD−7000RHを用いて測定し
た。樹脂成分を粉砕して得た粉末試料10mgについ
て、He流量100cm3/minの雰囲気中、昇温速度5℃
/minにおける加熱減量曲線を測定し5%減量を示す温
度を熱分解開始温度とした。測定結果は表1にまとめて
示す。<Example 1> 80 g of 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (A) (central glass)
-Perfluorononenyloxy-3,5-phthaloylbis (4- (4-cyanamidephenoxy) phenyl)
(C) (Manac) 20 g with methyl isobutyl ketone 10
It was dissolved in 0 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., and once the sample is melted, 250
The temperature was raised to ° C and pressure was applied. The characteristics of the obtained resin plate were evaluated. The relative permittivity is LF manufactured by Hewlett Packard
Using the impedance analyzer 4192A, JIS-
The capacitance of the sample was measured according to C-6481 and the relative permittivity was calculated. Regarding the coefficient of thermal expansion, using a thermomechanical property measuring device TM-3000 manufactured by Vacuum Riko Co., Ltd., a resin plate of 7 mm x 7 mm
Expansion coefficient (50-220) in the thickness direction of the sample cut into
C) was measured. The measurement was performed in a compression mode with a temperature rising rate of 2 ° C./min and a load of 10 g. Bending strength was measured according to JIS-C-6481, using Autograph DDS-5000 manufactured by Shimadzu Corporation. A sample cut out from a resin plate into a size of 50 mm × 5 mm was measured under the conditions of a fulcrum distance of 30 mm and a bending speed of 2 mm / min. The thermal decomposition starting temperature was measured using a high speed differential thermal balance TGD-7000RH manufactured by Vacuum Riko. About 10 mg of a powder sample obtained by crushing a resin component, a heating rate of 5 ° C. in an atmosphere with a He flow rate of 100 cm 3 / min.
The weight loss curve at 5 / min was measured, and the temperature at which the weight loss was 5% was defined as the thermal decomposition start temperature. The measurement results are summarized in Table 1.
【0063】[0063]
【表1】 [Table 1]
【0064】〈実施例2〉2,2−ビス(4−(4−マ
レイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80gと1−パーフルオロノネニルオキシ−3,5
−フタロイルビス(4−(4−シアナミドフェノキシ)
(C)(マナック)10g及び、4,4′−ジフェニル
メタンビスマレイミド(E)(三井東圧)10gをメチ
ルイソブチルケトン100gに溶かし、100℃,60
分還流下でプレポリマ化を行った。室温まで冷却後真空
乾燥により溶媒を除去し粉末状の試料を得た。得られた
試料を厚さ2mmのスペーサを用いてプレス成形により硬
化物の樹脂板を得た。硬化条件は150℃で試料を、一
旦、溶融した後、250℃に昇温し加圧した。得られた
樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解温度を
測定した。Example 2 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (manac) and 10 g of 4,4′-diphenylmethane bismaleimide (E) (Mitsui Toatsu) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C. and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0065】〈実施例3〉2,2−ビス(4−(4−マ
レイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80gと1−パーフルオロノネニルオキシ−3,5
−フタロイルビス(4−(4−シアナミドフェノキシ)
(C)(マナック)10g及び、4,4′−ジシアナミ
ドジフェニルエーテル(F)(マナック)10gをメチ
ルイソブチルケトン100gに溶かし、100℃,60
分還流下でプレポリマ化を行った。室温まで冷却後真空
乾燥により溶媒を除去し粉末状の試料を得た。得られた
試料を厚さ2mmのスペーサを用いてプレス成形により硬
化物の樹脂板を得た。硬化条件は150℃で試料を、一
旦、溶融した後、250℃に昇温し加圧した。得られた
樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解温度を
測定した。Example 3 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (Manac) and 10 g of 4,4'-dicyanamide diphenyl ether (F) (Manac) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0066】〈実施例4〉2,2−ビス(4−(4−マ
レイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80gと1−パーフルオロノネニルオキシ−3,5
−フタロイルビス(4−(4−シアナミドフェノキシ)
(C)(マナック)10g及び、4,4′−ジフェニル
メタンジイソシアネ−ト(G)(武田薬品)10gをメチ
ルイソブチルケトン100gに溶かし、100℃,60
分還流下でプレポリマ化を行った。室温まで冷却後真空
乾燥により溶媒を除去し粉末状の試料を得た。得られた
試料を厚さ2mmのスペーサを用いてプレス成形により硬
化物の樹脂板を得た。硬化条件は150℃で試料を,一
旦、溶融した後、250℃に昇温し加圧した。得られた
樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解温度を
測定した。Example 4 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
10 g of (C) (manac) and 10 g of 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) were dissolved in 100 g of methyl isobutyl ketone, and the mixture was heated at 100 ° C and 60 ° C.
Prepolymerization was carried out under reflux for minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0067】〈実施例5〉2,2−ビス(4−(4−マ
レイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80gと1−パーフルオロノネニルオキシ−3,5
−フタロイルビス(4−(4−シアナミドフェノキシ)
(C)(マナック)10g及び、ビスフェノールA型エ
ポキシ化合物DER323(H)(ダウケミカル)10
gをメチルイソブチルケトン100gに溶かし、100
℃,60分還流下でプレポリマ化を行った。室温まで冷
却後真空乾燥により溶媒を除去し粉末状の試料を得た。
得られた試料を厚さ2mmのスペーサを用いてプレス成形
により硬化物の樹脂板を得た。硬化条件は150℃で試
料を、一旦、溶融した後、250℃に昇温し加圧した。
得られた樹脂板の比誘電率,熱膨張率,曲げ強度,熱分
解温度を測定した。Example 5 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
(C) (Manac) 10 g and bisphenol A type epoxy compound DER323 (H) (Dow Chemical) 10
g to 100 g of methyl isobutyl ketone,
Prepolymerization was performed under reflux at 60 ° C for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample.
The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed.
The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0068】〈実施例6〉2,2−ビス(4−(4−マ
レイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80gと1−パーフルオロノネニルオキシ−3,5
−フタロイルビス(4−(4−シアナミドフェノキシ)
(C)(マナック)10g及び、p−ジビニルベンゼン
(I)(和光純薬)10gをメチルイソブチルケトン10
0gに溶かし、100℃,60分還流下でプレポリマ化
を行った。室温まで冷却後真空乾燥により溶媒を除去し
粉末状の試料を得た。得られた試料を厚さ2mmのスペー
サを用いてプレス成形により硬化物の樹脂板を得た。硬
化条件は150℃で試料を、一旦、溶融した後、250
℃に昇温し加圧した。得られた樹脂板の比誘電率,熱膨
張率,曲げ強度,熱分解温度を測定した。Example 6 2,2-bis (4- (4-maleimidophenoxy) phenyl) -1,1,1,3
80 g of 3,3-hexafluoropropane (A) (central glass) and 1-perfluorononenyloxy-3,5
-Phthaloylbis (4- (4-cyanamidephenoxy)
(C) (Manac) 10 g and p-divinylbenzene
(I) (Wako Pure Chemical Industries, Ltd.) 10 g of methyl isobutyl ketone 10
It was dissolved in 0 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., and once the sample is melted, 250
The temperature was raised to ° C and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0069】〈実施例7〉2,2−ビス(4−(4−マ
レイミド−2−トリフルオロメチルフェノキシ)フェニ
ル)−1,1,1,3,3,3−ヘキサフルオロプロパ
ン(B)(セントラル硝子)80gと1−パーフルオロ
ノネニルオキシ−3,5−フタロイルビス(4−(4−
シアナミドフェノキシ)(D)(マナック)20gをメ
チルイソブチルケトン100gに溶かし、100℃,6
0分還流下でプレポリマ化を行った。室温まで冷却後真
空乾燥により溶媒を除去し粉末状の試料を得た。得られ
た試料を厚さ2mmのスペーサを用いてプレス成形により
硬化物の樹脂板を得た。硬化条件は150℃で試料を、
一旦、溶融した後、250℃に昇温し加圧した。得られ
た樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解温度
を測定した。Example 7 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 20 g is melt | dissolved in 100 g of methyl isobutyl ketones, 100 degreeC and 6
Prepolymerization was carried out under reflux for 0 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C for the sample,
Once melted, the temperature was raised to 250 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0070】〈実施例8〉2,2−ビス(4−(4−マ
レイミド−2−トリフルオロメチルフェノキシ)フェニ
ル)−1,1,1,3,3,3−ヘキサフルオロプロパ
ン(B)(セントラル硝子)80gと1−パーフルオロ
ノネニルオキシ−3,5−フタロイルビス(4−(4−
シアナミドフェノキシ)(D)(マナック)10g及
び、4,4′−ジフェニルメタンビスマレイミド(E)
(三井東圧)10gをメチルイソブチルケトン100g
に溶かし、100℃,60分還流下でプレポリマ化を行
った。室温まで冷却後真空乾燥により溶媒を除去し粉末
状の試料を得た。得られた試料を厚さ2mmのスペーサを
用いてプレス成形により硬化物の樹脂板を得た。硬化条
件は150℃で試料を、一旦、溶融した後、250℃に
昇温し加圧した。得られた樹脂板の比誘電率,熱膨張
率,曲げ強度,熱分解温度を測定した。Example 8 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 10 g and 4,4'-diphenylmethane bismaleimide (E)
(Mitsui Toatsu) 10 g methyl isobutyl ketone 100 g
And was prepolymerized under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0071】〈実施例9〉2,2−ビス(4−(4−マ
レイミド−2−トリフルオロメチルフェノキシ)フェニ
ル)−1,1,1,3,3,3−ヘキサフルオロプロパ
ン(B)(セントラル硝子)80gと1−パーフルオロ
ノネニルオキシ−3,5−フタロイルビス(4−(4−
シアナミドフェノキシ)(D)(マナック)10g及
び、4,4′−ジシアナミドジフェニルエーテル(F)
(マナック)10gをメチルイソブチルケトン100g
に溶かし、100℃,60分還流下でプレポリマ化を行
った。室温まで冷却後真空乾燥により溶媒を除去し粉末
状の試料を得た。得られた試料を厚さ2mmのスペーサを
用いてプレス成形により硬化物の樹脂板を得た。硬化条
件は150℃で試料を、一旦、溶融した後、250℃に
昇温し加圧した。得られた樹脂板の比誘電率,熱膨張
率,曲げ強度,熱分解温度を測定した。Example 9 2,2-bis (4- (4-maleimido-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) ( 80 g of central glass) and 1-perfluorononenyloxy-3,5-phthaloylbis (4- (4-
Cyanamide phenoxy) (D) (Manac) 10 g and 4,4'-dicyanamide diphenyl ether (F)
(Manac) 10 g methyl isobutyl ketone 100 g
And was prepolymerized under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0072】〈実施例10〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80gと1−パーフルオ
ロノネニルオキシ−3,5−フタロイルビス(4−(4
−シアナミドフェノキシ)(D)(マナック)10g及
び、4,4′−ジフェニルメタンジイソシアネート
(G)(武田薬品)10gをメチルイソブチルケトン1
00gに溶かし、100℃,60分還流下でプレポリマ
化を行った。室温まで冷却後真空乾燥により溶媒を除去
し粉末状の試料を得た。得られた試料を厚さ2mmのスペ
ーサを用いてプレス成形により硬化物の樹脂板を得た。
硬化条件は150℃で試料を、一旦、溶融した後、25
0℃に昇温し加圧した。得られた樹脂板の比誘電率,熱
膨張率,曲げ強度,熱分解温度を測定した。<Embodiment 10> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamidephenoxy) (D) (Manac) and 10 g of 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) were added to methyl isobutyl ketone 1
It was dissolved in 00 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate.
The curing conditions are 150 ° C. and once the sample is melted,
The temperature was raised to 0 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0073】〈実施例11〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80gと1−パーフルオ
ロノネニルオキシ−3,5−フタロイルビス(4−(4
−シアナミドフェノキシ)(D)(マナック)10g及
び、ビスフェノールA型エポキシ化合物DER323
(H)(ダウケミカル)10gをメチルイソブチルケト
ン100gに溶かし、100℃,60分還流下でプレポ
リマ化を行った。室温まで冷却後真空乾燥により溶媒を
除去し粉末状の試料を得た。得られた試料を厚さ2mmの
スペーサを用いてプレス成形により硬化物の樹脂板を得
た。硬化条件は150℃で試料を、一旦、溶融した後、
250℃に昇温し加圧した。得られた樹脂板の比誘電
率,熱膨張率,曲げ強度,熱分解温度を測定した。<Embodiment 11> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamide phenoxy) (D) (Manac) 10 g and bisphenol A type epoxy compound DER323
10 g of (H) (Dow Chemical) was dissolved in 100 g of methyl isobutyl ketone, and prepolymerized at 100 ° C. under reflux for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing conditions are 150 ° C., after melting the sample once,
The temperature was raised to 250 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0074】〈実施例12〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80gと1−パーフルオ
ロノネニルオキシ−3,5−フタロイルビス(4−(4
−シアナミドフェノキシ)(D)(マナック)10g及
び、p−ジビニルベンゼン(I)(和光純薬)10gを
メチルイソブチルケトン100gに溶かし、100℃,
60分還流下でプレポリマ化を行った。室温まで冷却後
真空乾燥により溶媒を除去し粉末状の試料を得た。得ら
れた試料を厚さ2mmのスペーサを用いてプレス成形によ
り硬化物の樹脂板を得た。硬化条件は150℃で試料
を、一旦、溶融した後、250℃に昇温し加圧した。得
られた樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解
温度を測定した。<Embodiment 12> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 g and 1-perfluorononenyloxy-3,5-phthaloylbis ( 4- (4
-Cyanamidephenoxy) (D) (Manac) 10 g and p-divinylbenzene (I) (Wako Pure Chemical Industries, Ltd.) 10 g were dissolved in methyl isobutyl ketone 100 g,
Prepolymerization was carried out under reflux for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0075】〈比較例1〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80gと4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)2
0gをメチルイソブチルケトン100gに溶かし、10
0℃,60分還流下でプレポリマ化を行った。室温まで
冷却後真空乾燥により溶媒を除去し粉末状の試料を得
た。得られた試料を厚さ2mmのスペーサを用いてプレス
成形により硬化物の樹脂板を得た。硬化条件は150℃
で試料を、一旦、溶融した後、250℃に昇温し加圧し
た。得られた樹脂板の比誘電率,熱膨張率,曲げ強度,
熱分解温度を測定した。Comparative Example 1 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 g and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 2
Dissolve 0 g in 100 g of methyl isobutyl ketone,
Prepolymerization was performed under reflux at 0 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. Curing condition is 150 ℃
The sample was once melted, heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength,
The thermal decomposition temperature was measured.
【0076】〈比較例2〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80gと4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)10
g及び、4,4′−ジフェニルメタンジイソシアネート
(G)(武田薬品)10gをメチルイソブチルケトン1
00gに溶かし、100℃,60分還流下でプレポリマ
化を行った。室温まで冷却後真空乾燥により溶媒を除去
し粉末状の試料を得た。得られた試料を厚さ2mmのスペ
ーサを用いてプレス成形により硬化物の樹脂板を得た。
硬化条件は150℃で試料を、一旦、溶融した後、25
0℃に昇温し加圧した。得られた樹脂板の比誘電率,熱
膨張率,曲げ強度,熱分解温度を測定した。Comparative Example 2 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 g and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 10
g and 4,4'-diphenylmethane diisocyanate (G) (Takeda Yakuhin) 10 g with methyl isobutyl ketone 1
It was dissolved in 00 g and subjected to prepolymerization under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate.
The curing conditions are 150 ° C. and once the sample is melted,
The temperature was raised to 0 ° C. and pressure was applied. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0077】〈比較例3〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80gと4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)1
0g及び、ビスフェノールA型エポキシ化合物DER3
23(H)(ダウケミカル)10gをメチルイソブチル
ケトン100gに溶かし、100℃,60分還流下でプ
レポリマ化を行った。室温まで冷却後真空乾燥により溶
媒を除去し粉末状の試料を得た。得られた試料を厚さ2
mmのスペーサを用いてプレス成形により硬化物の樹脂板
を得た。硬化条件は150℃で試料を、一旦、溶融した
後、250℃に昇温し加圧した。得られた樹脂板の比誘
電率,熱膨張率,曲げ強度,熱分解温度を測定した。 〈比較例4〉4,4′−ジフェニルメタンビスマレイミ
ド(E)(三井東圧)80gと4,4′−ジシアナミド
ジフェニルエーテル(F)(マナック)10g及び、p
−ジビニルベンゼン(I)(和光純薬)10gをメチル
イソブチルケトン100gに溶かし、100℃,60分
還流下でプレポリマ化を行った。室温まで冷却後真空乾
燥により溶媒を除去し粉末状の試料を得た。得られた試
料を厚さ2mmのスペーサを用いてプレス成形により硬化
物の樹脂板を得た。硬化条件は150℃で試料を、一
旦、溶融した後、250℃に昇温し加圧した。得られた
樹脂板の比誘電率,熱膨張率,曲げ強度,熱分解温度を
測定した。Comparative Example 3 80 g of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 4,4'-
Dicyanamide diphenyl ether (F) (Manac) 1
0g and bisphenol A type epoxy compound DER3
10 g of 23 (H) (Dow Chemical) was dissolved in 100 g of methyl isobutyl ketone, and prepolymerization was performed under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The thickness of the obtained sample is 2
A resin plate of a cured product was obtained by press molding using a spacer of mm. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured. <Comparative Example 4> 80 g of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 10 g of 4,4'-dicyanamide diphenyl ether (F) (Manac) and p
Divinylbenzene (I) (Wako Pure Chemical Industries, Ltd.) (10 g) was dissolved in methyl isobutyl ketone (100 g), and prepolymerization was performed under reflux at 100 ° C. for 60 minutes. After cooling to room temperature, the solvent was removed by vacuum drying to obtain a powdery sample. The obtained sample was press-molded using a spacer having a thickness of 2 mm to obtain a cured resin plate. The curing condition was 150 ° C. The sample was once melted, then heated to 250 ° C. and pressed. The relative permittivity, thermal expansion coefficient, bending strength, and thermal decomposition temperature of the obtained resin plate were measured.
【0078】実施例,比較例で用いた化合物(A)〜
(I)は以下の通りであり、得られた硬化物の特性を表
1に示す。Compounds (A) used in Examples and Comparative Examples
(I) is as follows, and the properties of the obtained cured product are shown in Table 1.
【0079】[0079]
【化24】 [Chemical formula 24]
【0080】〈実施例13〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノキ
シ)(C)(マナック)20重量部、重合開始剤として
過酸化物0.5重量部よりなる樹脂組成物を溶媒ジメチ
ルホルムアミドに溶解し50%溶液を調整し、振盪攪拌
してワニスとして用いた。<Embodiment 13> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A resin composition comprising 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator was dissolved in a solvent dimethylformamide to obtain 50%. The solution was prepared, shaken and stirred and used as a varnish.
【0081】ワニスを補強材である日東紡製Tガラスク
ロス(厚さ60μm)に含浸塗工し、150℃の恒温空
気中で10分間乾燥しプリプレグを得た。得られたプリ
プレグ10枚を重ね、プレス中で圧力30kgf/c
m2 ,温度130℃で30分間加熱し、さらに250℃
で1時間接着硬化反応し、積層板を得た。銅箔ピール強
度の測定用試料としてはプリプレグ10枚を重ねたもの
の両面に銅箔(古河電工製,厚さ70μm)を重ね、同
様の条件で積層接着した。以上の方法で作製した試料に
ついて特性評価した。比誘電率は、ヒューレットパッカ
ード社製LFインピーダンスアナライザ4192Aを用
い、JIS−C−6481に従い試料の静電容量を測定
し比誘電率を計算した。銅箔ピール強度は不動工業製レ
オメータNRM−3101Dを用い、JIS−C−64
81に従い、引きはがし速度50mm/min の条件で垂直
方向の銅箔ピール強度を測定した。熱分解開始温度につ
いては、真空理工製高速示差熱天秤TGD−7000R
Hを用いて測定した。樹脂成分を粉砕して得た粉末試料
10mgについて、He流量100cm3/minの雰囲気
中、昇温速度5℃/min における加熱減量曲線を測定し
5%減量を示す温度を熱分解開始温度とした。熱膨張率
に関しては、真空理工製熱機械特性測定装置TM−30
00を用い、積層板から7mm×7mmに切り出した試料の
厚さ方向の熱膨張率(50−220℃)測定した。昇温
速度2℃/min ,荷重10gの圧縮モードで測定した。
難燃性の測定はUL−94により測定した。測定結果は
表2にまとめて示す。A varnish was impregnated and coated on a N glass material T glass cloth (thickness: 60 μm) which was a reinforcing material, and dried in constant temperature air at 150 ° C. for 10 minutes to obtain a prepreg. 10 sheets of the obtained prepreg are piled up, and pressure is 30 kgf / c in the press.
m 2, was heated for 30 minutes at 130 ° C., further 250 ° C.
After that, the adhesive was cured for 1 hour to obtain a laminated plate. As a sample for measuring the copper foil peel strength, 10 prepregs were stacked, and copper foil (manufactured by Furukawa Electric Co., Ltd., thickness 70 μm) was stacked on both surfaces and laminated and bonded under the same conditions. The characteristics of the sample manufactured by the above method were evaluated. The relative dielectric constant was calculated by measuring the capacitance of the sample according to JIS-C-6481 using an LF impedance analyzer 4192A manufactured by Hewlett-Packard Company. Copper foil peel strength is measured using Fudo Industrial Rheometer NRM-3101D according to JIS-C-64
According to No. 81, the peel strength of the copper foil in the vertical direction was measured under the condition of the peeling speed of 50 mm / min. Regarding the thermal decomposition start temperature, high-speed differential thermal balance TGD-7000R manufactured by Vacuum Riko Co., Ltd.
It was measured using H. About 10 mg of a powder sample obtained by crushing a resin component, a heating weight loss curve was measured at a temperature rising rate of 5 ° C./min in an atmosphere with a He flow rate of 100 cm 3 / min, and the temperature showing 5% weight loss was defined as the pyrolysis start temperature. .. Regarding the coefficient of thermal expansion, vacuum mechanical engineering thermomechanical property measuring device TM-30
No. 00 was used to measure the coefficient of thermal expansion (50-220 ° C.) in the thickness direction of the sample cut out from the laminated plate into 7 mm × 7 mm. The measurement was performed in a compression mode with a temperature rising rate of 2 ° C./min and a load of 10 g.
The flame retardancy was measured by UL-94. The measurement results are summarized in Table 2.
【0082】[0082]
【表2】 [Table 2]
【0083】〈実施例14〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノキ
シ)(C)(マナック)20重量部、重合開始剤として
過酸化物0.5重量部よりなる樹脂組成物を用いてワニ
スを調整した。ワニス調整法は実施例13に示した方法
に従った。このワニスを用いて実施例13と同様な方法
で補強材としてデュポン社製芳香族アミド系有機合成繊
維織布ケブラ49を用いてプリプレグ,積層板を作製
し、特性を評価した。結果を表2に示す。<Embodiment 14> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A varnish was prepared by using a resin composition containing 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The adjusting method was in accordance with the method shown in Example 13. Using this varnish, the aromatic amide type organic synthetic fiber woven Kevlar 49 made by DuPont as a reinforcing material was used as a reinforcing material for prepreg and lamination. A plate was prepared and its properties were evaluated, and the results are shown in Table 2.
【0084】〈実施例15〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)80重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、重合開始剤とし
て過酸化物0.5 重量部よりなる樹脂組成物を用いて
ワニスを調整した。ワニス調整法は実施例13に示した
方法に従った。このワニスを用いて実施例13と同様な
方法で補強材として日本アロマ製芳香族アミド系有機合
成繊維不織布GAU−505−50を用いてプリプレ
グ,積層板を作製し、特性を評価した。結果を表2に示
す。<Embodiment 15> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
80 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
A varnish was prepared using a resin composition comprising 20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The adjusting method was in accordance with the method shown in Example 13. Using this varnish, a prepreg was prepared in the same manner as in Example 13, using the aromatic amide organic synthetic fiber nonwoven fabric GAU-505-50 manufactured by Nippon Aroma Co. as a reinforcing material. A laminated plate was prepared and the characteristics were evaluated, and the results are shown in Table 2.
【0085】〈実施例16〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジフェニルメタンビスマレイミド(E)(三井東圧)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材として日東紡製T
ガラスクロス(厚さ60μm)を用いてプリプレグ,積
層板を作製し、特性を評価した。結果を表2に示す。Example 16 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, Nitto Boseki T was used as a reinforcing material in the same manner as in Example 13.
Using a glass cloth (thickness: 60 μm), a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.
【0086】〈実施例17〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジフェニルメタンビスマレイミド(E)(三井東圧)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材としてデュポン社
製芳香族アミド系有機合成繊維織布ケブラ49を用いて
プリプレグ,積層板を作製し、特性を評価した。結果を
表2に示す。Example 17 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.
【0087】〈実施例18〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジフェニルメタンビスマレイミド(E)(三井東圧)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材として日本アロマ
製芳香族アミド系有機合成繊維不織布GAU−505−
50を用いてプリプレグ,積層板を作製し、特性を評価
した。結果を表2に示す。<Embodiment 18> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Diphenylmethane bismaleimide (E) (Mitsui Toatsu) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber nonwoven fabric GAU-505 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
50 was used to prepare a prepreg and a laminated board, and the characteristics were evaluated. The results are shown in Table 2.
【0088】〈実施例19〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材として日東紡製T
ガラスクロス(厚さ60μm)を用いてプリプレグ,積
層板を作製し、特性を評価した。結果を表2に示す。Example 19 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, Nitto Boseki T was used as a reinforcing material in the same manner as in Example 13.
Using a glass cloth (thickness: 60 μm), a prepreg and a laminated board were produced and the characteristics were evaluated. The results are shown in Table 2.
【0089】〈実施例20〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材としてデュポン社
製芳香族アミド系有機合成繊維織布ケブラ49を用いて
プリプレグ,積層板を作製し、特性を評価した。結果を
表2に示す。<Embodiment 20> 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.
【0090】〈実施例21〉2,2−ビス(4−(4−
マレイミドフェノキシ)フェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパン(A)(セントラル硝
子)70重量部、1−パーフルオロノネニルオキシ−
3,5−フタロイルビス(4−(4−シアナミドフェノ
キシ)(C)(マナック)20重量部、及び4,4′−
ジシアナミドジフェニルエーテル(F)(マナック)1
0重量部と重合開始剤として過酸化物0.5 重量部より
なる樹脂組成物を用いてワニスを調整した。ワニス調整
法は実施例13に示した方法に従った。このワニスを用
いて実施例13と同様な方法で補強材として日本アロマ
製芳香族アミド系有機合成繊維不織布GAU−505−
50を用いてプリプレグ,積層板を作製し、特性を評価
した。結果を表2に示す。Example 21 2,2-bis (4- (4-
Maleimidophenoxy) phenyl) -1,1,1,3
70 parts by weight of 3,3-hexafluoropropane (A) (central glass), 1-perfluorononenyloxy-
20 parts by weight of 3,5-phthaloylbis (4- (4-cyanamidephenoxy) (C) (Manac), and 4,4′-
Dicyanamide diphenyl ether (F) (Manac) 1
A varnish was prepared using a resin composition containing 0 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber nonwoven fabric GAU-505 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
50 was used to prepare a prepreg and a laminated board, and the characteristics were evaluated. The results are shown in Table 2.
【0091】〈実施例22〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80重量部、1−パーフ
ルオロノネニルオキシ−3,5−フタロイルビス(4−
(4−シアナミドフェノキシ)(D)(マナック)20
重量部、重合開始剤として過酸化物0.5 重量部よりな
る樹脂組成物を用いてワニスを調整した。ワニス調整法
は実施例13に示した方法に従った。このワニスを用い
て実施例13と同様な方法で補強材として日東紡製Tガ
ラスクロス(厚さ60μm)を用いてプリプレグ,積層
板を作製し、特性を評価した。結果を表2に示す。<Embodiment 22> 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminated board were manufactured by using Nitto Boseki T glass cloth (thickness 60 μm) as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.
【0092】〈実施例23〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80重量部、1−パーフ
ルオロノネニルオキシ−3,5−フタロイルビス(4−
(4−シアナミドフェノキシ)(D)(マナック)20
重量部、重合開始剤として過酸化物0.5 重量部よりな
る樹脂組成物を用いてワニスを調整した。ワニス調整法
は実施例13に示した方法に従った。このワニスを用い
て実施例13と同様な方法で補強材としてデュポン社製
芳香族アミド系有機合成繊維織布ケブラ49を用いてプ
リプレグ,積層板を作製し、特性を評価した。結果を表
2に示す。Example 23 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.
【0093】〈実施例24〉2,2−ビス(4−(4−
マレイミド−2−トリフルオロメチルフェノキシ)フェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン(B)(セントラル硝子)80重量部、1−パーフ
ルオロノネニルオキシ−3,5−フタロイルビス(4−
(4−シアナミドフェノキシ)(D)(マナック)20
重量部、重合開始剤として過酸化物0.5 重量部よりな
る樹脂組成物を用いてワニスを調整した。ワニス調整法
は実施例13に示した方法に従った。このワニスを用い
て実施例13と同様な方法で補強材として日本アロマ製
芳香族アミド系有機合成繊維不織布GAU−505−5
0を用いてプリプレグ,積層板を作製し、特性を評価し
た。結果を表2に示す。Example 24 2,2-bis (4- (4-
Maleimide-2-trifluoromethylphenoxy) phenyl) -1,1,1,3,3,3-hexafluoropropane (B) (Central Glass) 80 parts by weight, 1-perfluorononenyloxy-3,5- Phthaloylbis (4-
(4-Cyanamide phenoxy) (D) (Manac) 20
A varnish was prepared by using a resin composition comprising 1 part by weight and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, the aromatic amide organic synthetic fiber non-woven fabric GAU-505-5 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
0 was used to prepare a prepreg and a laminated plate, and the characteristics were evaluated. The results are shown in Table 2.
【0094】〈比較例5〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80重量部と4,
4′−ジシアナミドジフェニルエーテル(F)(マナッ
ク)20重量部、重合開始剤として過酸化物0.5 重量
部よりなる樹脂組成物を用いてワニスを調整した。ワニ
ス調整法は実施例13に示した方法に従った。このワニ
スを用いて実施例13と同様な方法で補強材として日東
紡製Tガラスクロス(厚さ60μm)を用いてプリプレ
グ,積層板を作製し、特性を評価した。結果を表2に示
す。Comparative Example 5 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 parts by weight and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminated board were manufactured by using Nitto Boseki T glass cloth (thickness 60 μm) as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated. The results are shown in Table 2.
【0095】〈比較例6〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80重量部と4,
4′−ジシアナミドジフェニルエーテル(F)(マナッ
ク)20重量部、重合開始剤として過酸化物0.5 重量
部よりなる樹脂組成物を用いてワニスを調整した。ワニ
ス調整法は実施例13に示した方法に従った。このワニ
スを用いて実施例13と同様な方法で補強材としてデュ
ポン社製芳香族アミド系有機合成繊維織布ケブラ49を
用いてプリプレグ,積層板を作製し、特性を評価した。
結果を表2に示す。Comparative Example 6 80 parts by weight of 4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 parts by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a prepreg and a laminate were prepared by using the aromatic amide organic synthetic fiber woven Kevlar 49 manufactured by DuPont as a reinforcing material in the same manner as in Example 13, and the characteristics were evaluated.
The results are shown in Table 2.
【0096】〈比較例7〉4,4′−ジフェニルメタン
ビスマレイミド(E)(三井東圧)80重量部と4,
4′−ジシアナミドジフェニルエ−テル(F)(マナッ
ク)20重量部、重合開始剤として過酸化物0.5 重量
部よりなる樹脂組成物を用いてワニスを調整した。ワニ
ス調整法は実施例13に示した方法に従った。このワニ
スを用いて実施例13と同様な方法で補強材として日本
アロマ製芳香族アミド系有機合成繊維不織布GAU−5
05−50を用いてプリプレグ,積層板を作製し、特性
を評価した。結果を表2に示す。<Comparative Example 7>4,4'-diphenylmethane bismaleimide (E) (Mitsui Toatsu) 80 parts by weight and 4,
A varnish was prepared using a resin composition containing 20 parts by weight of 4'-dicyanamide diphenyl ether (F) (Manac) and 0.5 part by weight of a peroxide as a polymerization initiator. The varnish preparation method was according to the method shown in Example 13. Using this varnish, a aromatic amide organic synthetic fiber nonwoven fabric GAU-5 manufactured by Nippon Aroma Co., Ltd. was used as a reinforcing material in the same manner as in Example 13.
The prepreg and the laminated board were produced using 05-50, and the characteristic was evaluated. The results are shown in Table 2.
【0097】〈比較例8〉比較例として、ポリテトラフ
ルオロエチレン系銅張り積層板である松下電工製R47
37について実施例13と同様に特性評価した。<Comparative Example 8> As a comparative example, a polytetrafluoroethylene-based copper clad laminate R47 manufactured by Matsushita Electric Works, Ltd.
37 was evaluated in the same manner as in Example 13.
【0098】〈比較例9〉比較例として、ガラスポリイ
ミド系銅張り積層板である日立化成製MCL−I−67
について実施例13と同様に特性評価した。<Comparative Example 9> As a comparative example, a glass polyimide copper-clad laminate MCL-I-67 manufactured by Hitachi Chemical Co., Ltd.
Was evaluated in the same manner as in Example 13.
【0099】〈比較例10〉比較例として、ガラスエポ
キシ系銅張り積層板である日立化成製MCL−E−67
について実施例13と同様に特性評価した。Comparative Example 10 As a comparative example, a glass epoxy copper-clad laminate MCL-E-67 manufactured by Hitachi Chemical Co., Ltd.
Was evaluated in the same manner as in Example 13.
【0100】以下、実施例13ないし24に示した積層
材料を用いて配線板を作成した実施例を示す。The following is an example in which a wiring board was prepared using the laminated materials shown in Examples 13 to 24.
【0101】〈実施例25〉実施例13によりえられた
プリプレグを用いて、両面に銅箔(70μm)をプレス
中で圧力30kgf/cm2 ,温度130℃で30分間加
熱し、さらに250℃で一時間接着硬化させ、銅張り積
層板を得た。この銅張り積層板の両面に回路を形成し、
プリプレグを介して積層接着し、LSIを搭載するピン
グリッドアレイ基板を作成した。この基板は6層構造か
ら成り、それぞれ2層の表面層,電源供給層,信号層を
有する。本実施例の層構成を図1に示す。Example 25 Using the prepreg obtained in Example 13, copper foil (70 μm) is heated on both sides in a press at a pressure of 30 kgf / cm 2 and a temperature of 130 ° C. for 30 minutes, and further at 250 ° C. The adhesive was cured for 1 hour to obtain a copper-clad laminate. Form circuits on both sides of this copper-clad laminate,
A pin grid array substrate on which an LSI is mounted was created by laminating and adhering via a prepreg. This substrate has a six-layer structure, and each has two surface layers, a power supply layer and a signal layer. The layer structure of this example is shown in FIG.
【0102】〈実施例26〉実施例13により得られた
プリプレグを用い、実施例25と同様にLSIを搭載す
るマイクロチップキャリア基板を作成した。この基板は
6層構造から成り、それぞれ2層の表面層,電源供給
層,信号層を有する。<Example 26> Using the prepreg obtained in Example 13, a microchip carrier substrate on which an LSI was mounted was prepared in the same manner as in Example 25. This substrate has a six-layer structure, and each has two surface layers, a power supply layer and a signal layer.
【0103】〈実施例27〉実施例13により得られた
プリプレグを用い、実施例25と同様な方法で実施例2
6により得られたマイクロチップキャリア基板を搭載す
るモジュール基板を作成した。この基板は表面層2層,
電源供給層10層,信号層16層,拡大層8層から成る
36層構造を有する。また、この基板はマイクロチップ
キャリア基板を81個(9×9)搭載可能である。Example 27 Example 2 was carried out in the same manner as in Example 25 using the prepreg obtained in Example 13.
A module substrate on which the microchip carrier substrate obtained in No. 6 is mounted was created. This substrate has two surface layers,
It has a 36-layer structure including 10 power supply layers, 16 signal layers, and 8 expansion layers. Also, 81 microchip carrier substrates (9 × 9) can be mounted on this substrate.
【0104】〈実施例28〉実施例13により得られた
プリプレグを用い、実施例25と同様な方法で実施例2
7により得られたモジュール基板を搭載する大面積基板
を作成した。この基板は表面層2層,電源供給層20
層,信号層24層,拡大層8層から成る54層構造を有
する。また、この基板はモジュール基板を64個(8×
8)搭載可能である。Example 28 Example 2 was carried out in the same manner as in Example 25 using the prepreg obtained in Example 13.
A large area substrate on which the module substrate obtained in No. 7 is mounted was created. This substrate has two surface layers and a power supply layer 20.
It has a 54-layer structure consisting of 24 layers of signal layers, and 8 layers of expansion layers. This board also has 64 module boards (8x
8) Can be installed.
【0105】〈実施例29〉実施例15により得られた
プリプレグを用い、実施例25と同様な方法で実施例2
7により得られたモジュール基板を搭載する大面積基板
を作成した。この基板は表面層2層,電源供給層16
層,信号層20層,拡大層8層から成る46層構造を有
する。また、この基板はモジュール基板を36個(6×
6)搭載可能である。Example 29 Example 2 is carried out in the same manner as in Example 25 using the prepreg obtained in Example 15.
A large area substrate on which the module substrate obtained in No. 7 is mounted was created. This substrate has two surface layers and a power supply layer 16
It has a 46-layer structure including a layer, 20 signal layers, and 8 expansion layers. This board also has 36 module boards (6x
6) Can be installed.
【0106】上記実施例に示すように、本発明により低
誘電率かつ高密度実装が可能となった。As shown in the above embodiment, the present invention enables low dielectric constant and high density mounting.
【0107】[0107]
【発明の効果】本発明の含フッ素樹脂は耐熱材料として
優れているイミド化合物に接着性を向上させるための極
性部位と、低誘電率化を計るためのフッ素基を導入した
化合含フッ素シアナミドを用いたものである。フッ素基
を構造中に多く取り込むことにより得られる硬化物のモ
ル比容を増加させ、低誘電率化を図ることができた。さ
らにフッ素基は炭素との結合解離エネルギが大きいた
め、耐熱性の目安である熱分解温度の向上,機械的強度
の向上も同時に図ることができた。また、シアナミド基
は速硬化性であることから作業性が優れる。以上、含フ
ッ素シアナミドと含フッ素イミドから成る熱硬化性樹脂
は成形性に優れ、かつ得られる硬化物は耐熱性,機械的
特性に優れていることが確認できた。さらに絶縁材料の
電気特性として重要な比誘電率も小さくすることがで
き、モ−ルド材,配線基板,LSIの層間絶縁膜等の低
誘電率が要求される分野に好適な材料となることが期待
できる。この多層板により構成した計算機は、絶縁層の
低誘電率化及び高密度多層化が可能になり、演算実行速
度が向上する。EFFECT OF THE INVENTION The fluorine-containing resin of the present invention is a compound containing fluorine-containing cyanamide in which an imide compound which is excellent as a heat-resistant material has a polar moiety for improving adhesiveness and a fluorine group for lowering the dielectric constant. Used. It was possible to increase the molar specific volume of the cured product obtained by incorporating a large amount of fluorine groups into the structure, and to lower the dielectric constant. Further, since the fluorine group has a large bond dissociation energy with carbon, it was possible to improve the thermal decomposition temperature, which is a measure of heat resistance, and mechanical strength at the same time. Further, since the cyanamide group is fast-curing, workability is excellent. As described above, it was confirmed that the thermosetting resin composed of the fluorinated cyanamide and the fluorinated imide had excellent moldability, and the obtained cured product had excellent heat resistance and mechanical properties. Further, the relative permittivity, which is important for the electrical characteristics of the insulating material, can be reduced, and it can be a material suitable for fields requiring a low permittivity such as a mold material, a wiring board, and an interlayer insulating film of an LSI. Can be expected. In the computer configured with this multilayer board, the dielectric constant of the insulating layer and the density of the insulating layer can be increased, and the operation execution speed is improved.
【図1】本発明の一実施例である多層プリント板の斜視
図。FIG. 1 is a perspective view of a multilayer printed board according to an embodiment of the present invention.
1…基板、2…回路、3…プリプレグシート、4…スル
ーホール。1 ... Substrate, 2 ... Circuit, 3 ... Prepreg sheet, 4 ... Through hole.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08L 79/08 LRE 9285−4J H01B 3/30 C 9059−5G H01L 23/12 // C08L 25:18 9166−4J (72)発明者 天羽 悟 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 川井 良憲 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内 (72)発明者 高橋 昭雄 茨城県日立市久慈町4026番地 株式会社日 立製作所日立研究所内─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification number Internal reference number FI technical display location C08L 79/08 LRE 9285-4J H01B 3/30 C 9059-5G H01L 23/12 // C08L 25: 18 9166-4J (72) Inventor Satoru Amaba 4026 Kuji Town, Hitachi City, Hitachi, Ibaraki Prefecture Hitachi Research Laboratory, Inc. (72) Yoshinori Kawai 4026 Kuji Town, Hitachi City, Ibaraki Institute Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi, Ltd.
Claims (27)
は1〜4の整数を示す。)で表されるビスマレイミド化
合物と、一般式(2) 【化2】 (式中、C9F17 基は二重結合を一個もつパーフルオロ
ノネニル基を、Xはエステル結合、あるいはエーテル結
合を含む2価の基を示す。)で表されるビスシアナミド
化合物を含むことを特徴とする熱硬化性樹脂組成物。1. A general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A thermosetting resin composition comprising:
記ビスシアナミド化合物を混合比95:5〜5:95で
用いる熱硬化性樹脂組成物。2. A thermosetting resin composition, wherein the bismaleimide compound of claim 1 and the biscyanamide compound are used in a mixing ratio of 95: 5 to 5:95.
は1〜4の整数を示す。)で表されるビスマレイミド化
合物と、一般式(2) 【化4】 (式中、C9F17 基は二重結合を一個もつパーフルオロ
ノネニル基を、Xはエステル結合、あるいはエーテル結
合を含む2価の基を示す。)で表されるビスシアナミド
化合物及び、マレイミド化合物,シアナミド化合物,シ
アナト化合物,イソシアナト化合物,エポキシ化合物,
ビニル化合物の中の少なくとも一種類を含むことを特徴
とする熱硬化性樹脂組成物。3. General formula (1): (In the formula, R represents hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.), And a biscyanamide compound, Maleimide compound, cyanamide compound, cyanato compound, isocyanato compound, epoxy compound,
A thermosetting resin composition comprising at least one kind of a vinyl compound.
組成物を溶媒に溶解し、均一なワニスにより作製する樹
脂組成物。4. The resin composition according to claim 1, 2 or 3, wherein the resin composition is dissolved in a solvent to prepare a uniform varnish.
は1〜4の整数を示す。)で表されるビスマレイミド化
合物と、一般式(2) 【化6】 (式中、C9F17 基は二重結合を一個もつパーフルオロ
ノネニル基を、Xはエステル結合、あるいはエーテル結
合を含む2価の基を示す。)で表されるビスシアナミド
化合物を用いて多重結合の重合反応により三次元架橋硬
化物を得ることを特徴とする樹脂硬化物の製造方法。5. A compound represented by the general formula (1): (In the formula, R represents hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A method for producing a cured resin product, characterized in that a three-dimensional crosslinked cured product is obtained by a polymerization reaction of multiple bonds.
加熱重合である樹脂硬化物の製造方法。6. The method for producing a resin cured product according to claim 5, wherein the polymerization reaction of multiple bonds is heat polymerization.
アルコキシ化合物等のアニオン重合開始剤の存在下での
重合である樹脂硬化物の製造方法。7. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.
過酸化物等のラジカル重合開始剤の存在下での重合であ
る樹脂硬化物の製造方法。8. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of the multiple bonds is polymerization in the presence of a radical polymerization initiator such as peroxide.
UV照射等の光重合である樹脂硬化物の製造方法。9. The method for producing a cured resin product according to claim 5, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.
は1〜4の整数を示す。)で表されるビスマレイミド化
合物と、一般式(2) 【化8】 (式中、C9F17 基は二重結合を一個もつパーフルオロ
ノネニル基を、Xはエステル結合、あるいはエーテル結
合を含む2価の基を示す。)で表されるビスシアナミド
化合物を含む樹脂組成物を多重結合の重合反応により三
次元架橋して得られる硬化物。10. A compound represented by the general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) A cured product obtained by three-dimensionally crosslinking a resin composition by a polymerization reaction of multiple bonds.
応が加熱重合である樹脂硬化物。11. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is heat polymerization.
応がアルコキシ化合物等のアニオン重合開始剤の存在下
での重合である樹脂硬化物。12. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of an anionic polymerization initiator such as an alkoxy compound.
応が過酸化物等のラジカル重合開始剤の存在下での重合
である樹脂硬化物。13. The resin cured product according to claim 10, wherein the polymerization reaction of multiple bonds is polymerization in the presence of a radical polymerization initiator such as a peroxide.
応がUV照射等の光重合である樹脂硬化物。14. The cured resin product according to claim 10, wherein the polymerization reaction of multiple bonds is photopolymerization such as UV irradiation.
が3以下である硬化物。15. The cured product according to claim 10, which has a relative dielectric constant of 3 or less.
は1〜4の整数を示す。)で表されるビスマレイミド化
合物と、一般式(2) 【化10】 (式中、C9F17 基は二重結合を一個もったパーフルオ
ロノネニル基を、Xはエステル結合、あるいはエーテル
結合を含む2価の基を示す。)で表されるビスシアナミ
ド化合物を含む樹脂組成物を、多重結合の重合反応によ
り三次元架橋して得られる硬化物を用いた電気絶縁体。16. A compound represented by the general formula (1): (In the formula, R is hydrogen, an alkyl group, halogen, n
Represents an integer of 1 to 4. ) And a bismaleimide compound represented by the general formula (2): (In the formula, the C 9 F 17 group is a perfluorononenyl group having one double bond, and X is a divalent group containing an ester bond or an ether bond.) An electrical insulator using a cured product obtained by three-dimensionally crosslinking a resin composition containing the same by a polymerization reaction of multiple bonds.
組成物を補強材である無機繊維布に含浸させて得られる
プリプレグ。17. A prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
組成物を補強材である有機繊維布に含浸させて得られる
プリプレグ。18. A prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
組成物を用いた積層材料。19. A laminate material using the resin composition according to claim 1, 2, 3 or 4.
組成物を他の樹脂成分と共に用いた積層材料。20. A laminated material using the resin composition according to claim 1, 2, 3 or 4 together with other resin components.
組成物を補強材である無機繊維布に含浸させて得られる
プリプレグを積層接着して得られる積層材料。21. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an inorganic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
組成物を補強材である有機繊維布に含浸させて得られる
プリプレグを積層接着して得られる積層材料。22. A laminated material obtained by laminating and adhering a prepreg obtained by impregnating an organic fiber cloth as a reinforcing material with the resin composition according to claim 1, 2, 3 or 4.
及び該組成物を用いた積層材料により構成される配線
板。23. A wiring board comprising the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.
及び該組成物を用いた積層材料により構成される大面積
基板。24. A large-area substrate composed of the resin composition according to claim 1 and a laminated material using the composition.
及び該組成物を用いた積層材料により構成されるモジュ
ール基板。25. A module substrate composed of the resin composition according to claim 1 and a laminated material using the composition.
及び該組成物を用いた積層材料により構成されるマイク
ロチップキャリア基板。26. A microchip carrier substrate composed of the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.
及び該組成物を用いた積層材料により構成されるピング
リッドアレイ基板。27. A pin grid array substrate composed of the resin composition according to any one of claims 1 to 22 and a laminated material using the composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30151791A JPH05140305A (en) | 1991-11-18 | 1991-11-18 | Fluorine-containing biscyamide resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30151791A JPH05140305A (en) | 1991-11-18 | 1991-11-18 | Fluorine-containing biscyamide resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05140305A true JPH05140305A (en) | 1993-06-08 |
Family
ID=17897885
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30151791A Pending JPH05140305A (en) | 1991-11-18 | 1991-11-18 | Fluorine-containing biscyamide resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05140305A (en) |
-
1991
- 1991-11-18 JP JP30151791A patent/JPH05140305A/en active Pending
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