JP2001294689A - Prepreg and laminated board - Google Patents
Prepreg and laminated boardInfo
- Publication number
- JP2001294689A JP2001294689A JP2000113154A JP2000113154A JP2001294689A JP 2001294689 A JP2001294689 A JP 2001294689A JP 2000113154 A JP2000113154 A JP 2000113154A JP 2000113154 A JP2000113154 A JP 2000113154A JP 2001294689 A JP2001294689 A JP 2001294689A
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- bis
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Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Inorganic Insulating Materials (AREA)
- Organic Insulating Materials (AREA)
- Insulating Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐燃性に優れ、か
つ電気特性や耐熱性の良好な樹脂組成物からなる、ハロ
ゲンフリーの電気絶縁材料のプリプレグ及び積層板に関
する。本発明で用いる樹脂組成物は、得られる硬化物の
耐燃性や電気特性が良好で、耐吸湿性、耐熱性に優れて
いることから、電気絶縁材料用途への使用に好適であ
る。該樹脂組成物を用いた積層板は、ハロゲンフリー、
かつリンフリーであり、その耐燃性は、ＵＬ規格94Ｖ-0
レベルを満足しており、焼却時にダイオキシンやホスフ
ィンが発生することのない、環境にやさしい電気絶縁材
料である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg and a laminate of a halogen-free electric insulating material, comprising a resin composition having excellent flame resistance and good electric characteristics and heat resistance. The resin composition used in the present invention is suitable for use in electric insulating materials because the cured product obtained has good flame resistance and electrical properties, and is excellent in moisture absorption resistance and heat resistance. Laminates using the resin composition are halogen-free,
And it is phosphorus-free, and its flame resistance is UL standard 94V-0
It is an environmentally friendly electrical insulating material that meets the level and does not generate dioxin or phosphine during incineration.
【０００２】[0002]
【従来技術】電子機器のプリント配線材料として、 エ
ポキシ樹脂系やＢＴ（ビスマレイミド／トリアジン）樹
脂系を用いた積層板が広く使用されており、これらの難
燃化の手法としては、臭素系化合物を配合した処方が一
般的である。近年、臭素系難燃剤を焼却した際に、毒性
の強い臭素化ジベンゾダイオキシンやジベンゾフランの
発生が確認され、いわゆる環境問題から、臭素系難燃剤
に対する種々の規制が論議されている。この結果, 熱可
塑性樹脂の分野では、臭素系難燃剤の替わりに、リン系
の難燃剤の使用が実用化されている。エポキシ樹脂ベー
スのプリント配線材料でも、臭素化エポキシ樹脂を削除
する方向で、配合の面から各種難燃剤が検討されてお
り、種々の提案が行われている。現在提案されている事
例では、リン系の難燃剤を使用する手法が主流である
が、リン系難燃剤の使用は、機械的、化学的、電気的な
特性を、著しく低下させるだけでなく、焼却時には、有
毒ガスの発生が避けられず、その使用については、懸念
があるため、臭素系難燃剤のみならず、リン系難燃剤も
使用せず、耐燃性に優れた材料の出現が強く要望されて
いる。2. Description of the Related Art As printed wiring materials for electronic equipment, laminated boards using epoxy resin or BT (bismaleimide / triazine) resin are widely used. Is generally used. In recent years, it has been confirmed that highly toxic brominated dibenzodioxins and dibenzofurans are generated when a brominated flame retardant is incinerated, and various regulations on brominated flame retardants have been discussed due to so-called environmental problems. As a result, in the field of thermoplastic resins, the use of phosphorus-based flame retardants instead of brominated flame retardants has been put to practical use. Even in the case of epoxy resin-based printed wiring materials, various flame retardants have been studied from the aspect of formulation in the direction of eliminating the brominated epoxy resin, and various proposals have been made. In the cases currently proposed, the method using phosphorus-based flame retardants is the mainstream, but the use of phosphorus-based flame retardants not only significantly reduces mechanical, chemical and electrical properties, During incineration, generation of toxic gas is unavoidable, and there is concern about its use. Therefore, the use of not only brominated flame retardants but also phosphorus-based flame retardants and the emergence of materials with excellent flame resistance is strongly demanded. Have been.
【０００３】[0003]
【発明が解決しようとする課題】これまでのエポキシ樹
脂系やＢＴ樹脂系の難燃性積層材料では、通常臭素化エ
ポキシ樹脂などの臭素系化合物を配合してプリプレグや
積層板が製造されていることから、環境問題をクリヤー
できる耐燃性の積層材料は、ほとんど見当たらない。本
発明は、これらの状況の中、ハロゲンフリーで、かつリ
ンフリーであり、しかも、耐燃性が良好で、電気特性や
耐熱性の優れたＢＴ樹脂系のプリプレグ及び積層板の提
供を目的とする。In the conventional flame-retardant laminated materials of epoxy resin and BT resin, prepregs and laminates are usually produced by blending a bromine compound such as a brominated epoxy resin. Therefore, there is hardly any flame-resistant laminated material that can eliminate environmental problems. An object of the present invention is to provide a BT resin-based prepreg and a laminate, which are halogen-free and phosphorus-free, have good flame resistance, and have excellent electric characteristics and heat resistance in these circumstances. .
【０００４】[0004]
【課題を解決するための手段】本発明者らは、種々検討
を行った結果、特定のビスマレイミド化合物とシアン酸
エステル化合物に無機系難燃剤を配合し、必要に応じて
エポキシ樹脂を併用したＢＴ樹脂系組成物から得られる
積層材料は、耐燃性に優れ、かつ電気特性や耐熱性が良
好であることを見出し、本発明を完成するに至った。即
ち、本発明は、下記式（１）As a result of various studies, the present inventors have formulated an inorganic flame retardant into a specific bismaleimide compound and a cyanate ester compound, and optionally used an epoxy resin in combination. The laminated material obtained from the BT resin-based composition has been found to be excellent in flame resistance and excellent in electrical characteristics and heat resistance, and has completed the present invention. That is, the present invention provides the following formula (1)
【化２】 （Ｒ1は水素またはアルキル基、Ｒ2はアルキル基を示
す）に示す構造単位を有するビスマレイミド化合物
（I）、1分子中に２個以上のシアナト基を有するシアン
酸エステル化合物（II）、無機系難燃剤（III）を必須
成分として含有し、ビスマレイミド化合物（I）とシア
ン酸エステル化合物（II）の配合割合が、各々４０〜８
５重量部、１５〜６０重量部である樹脂組成物を、基材
に含浸または塗布したことを特徴とするプリプレグ、並
びに該プリプレグを硬化して得られる電気絶縁材料用の
積層板または金属箔張り積層板を提供する。Embedded image (R 1 represents hydrogen or an alkyl group, R 2 represents an alkyl group), a bismaleimide compound (I) having a structural unit represented by the following formula, a cyanate compound (II) having two or more cyanato groups in one molecule, An inorganic flame retardant (III) is contained as an essential component, and the compounding ratio of the bismaleimide compound (I) and the cyanate ester compound (II) is 40 to 8 each.
A prepreg characterized by impregnating or applying 5 parts by weight, 15 to 60 parts by weight of a resin composition to a base material, and a laminate or metal foil cladding for an electrical insulating material obtained by curing the prepreg Provide a laminate.
【０００５】[0005]
【発明の実施の形態】本発明において使用されるビスマ
レイミド化合物（I）は、式（１）に示す構造単位を有
するビスマレイミド化合物であれば、特に限定されるも
のではない。その代表的な例としては、ビス（３−メチ
ルー４−マレイミドフェニル）メタン、ビス（３−エチ
ルー４−マレイミドフェニル）メタン、ビス（３、５−
ジメチルー４−マレイミドフェニル）メタン、ビス（３
−エチルー５−メチルー４−マレイミドフェニル）メタ
ン、ビス（３、５−ジエチルー４−マレイミドフェニ
ル）メタン、これらビスマレイミド化合物のプレポリマ
ー、もしくはビスマレイミド化合物とアミン化合物のプ
レポリマーなどが挙げられ、1種もしくは2種以上を適宜
混合して使用することも可能である。より好適なものと
しては、ビス（３、５−ジメチルー４−マレイミドフェ
ニル）メタン、ビス（３−エチルー５−メチルー４−マ
レイミドフェニル）メタン、ビス（３、５−ジエチルー
４−マレイミドフェニル）メタンが挙げられる。ビスマ
レイミド化合物（I）の配合量は、ビスマレイミド化合
物（I）とシアン酸エステル化合物（II）との合計量１
００重量部に対し、４０〜８５重量部、好ましくは５０
〜８０重量部である。上記範囲の下限未満では耐燃性が
不足し、上限を超えると反応性がが低下するため、本発
明の目的に適しない。BEST MODE FOR CARRYING OUT THE INVENTION The bismaleimide compound (I) used in the present invention is not particularly limited as long as it is a bismaleimide compound having a structural unit represented by the formula (1). Representative examples include bis (3-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis (3,5-
Dimethyl-4-maleimidophenyl) methane, bis (3
-Ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, a prepolymer of these bismaleimide compounds, or a prepolymer of a bismaleimide compound and an amine compound. Species or a mixture of two or more species may be used as appropriate. More preferred are bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane. No. The blending amount of the bismaleimide compound (I) is 1 in total of the bismaleimide compound (I) and the cyanate ester compound (II).
40 to 85 parts by weight, preferably 50
８０80 parts by weight. If the amount is less than the lower limit of the above range, the flame resistance is insufficient, and if the amount exceeds the upper limit, the reactivity is reduced, so that it is not suitable for the purpose of the present invention.
【０００６】本発明において使用されるシアン酸エステ
ル化合物（II）は、1分子中に２個以上のシアナト基を
有するシアン酸エステル化合物であれば、特に限定され
るものではない。その具体例としては、1,3-又は1,4-ジ
シアナトベンゼン、1,3,5-トリシアナトベンゼン、1,3
-、1,4-、1,6-、1,8-、2,6-又は2,7-ジシアナトナフタ
レン、1,3,6-トリシアナトナフタレン、4,4-ジシアナト
ビフェニル、ビス(4-ジシアナトフェニル)メタン、2,2-
ビス(4-シアナトフェニル)プロパン、ビス(4-シアナト
フェニル)エーテル、ビス(4-シアナトフェニル)チオエ
ーテル、ビス(4-シアナトフェニル)スルホン、およびノ
ボラックとハロゲン化シアンとの反応により得られるシ
アン酸エステル化合物などが挙げられ、1種もしくは2種
以上を適宜混合して使用することも可能である。また、
これらシアン酸エステル化合物のシアナト基の三量化に
よって形成されるトリアジン環を有する重量平均分子量
500〜5,000 のプレポリマーが、より好適に使用され
る。このプレポリマーは、上記のシアン酸エステルモノ
マーを、例えば鉱酸、ルイス酸などの酸類、ナトリウム
アルコラートなど、第三級アミン類などの塩基、炭酸ナ
トリウムなどの塩類などを触媒として重合させることに
より得られる。このプレポリマー中には一部未反応のモ
ノマーも含まれており、モノマーとプレポリマーとの混
合物の形態をしており、このような原料は本発明の用途
に好適である。[0006] The cyanate compound (II) used in the present invention is not particularly limited as long as it is a cyanate compound having two or more cyanato groups in one molecule. Specific examples thereof include 1,3- or 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3
-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4-dicyanatobiphenyl, bis ( 4-dicyanatophenyl) methane, 2,2-
Bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and the reaction of novolak with cyanogen halide The obtained cyanate ester compound and the like can be mentioned, and it is also possible to use one kind or two or more kinds as appropriate. Also,
Weight average molecular weight having a triazine ring formed by trimerization of a cyanato group of these cyanate compounds
500-5,000 prepolymers are more preferably used. This prepolymer is obtained by polymerizing the above-mentioned cyanate ester monomer with a catalyst such as an acid such as a mineral acid or a Lewis acid, a base such as a tertiary amine such as sodium alcoholate, or a salt such as sodium carbonate as a catalyst. Can be The prepolymer also contains some unreacted monomers and is in the form of a mixture of the monomer and the prepolymer, and such a raw material is suitable for the use of the present invention.
【０００７】シアン酸エステル化合物（II）の配合量
は、ビスマレイミド化合物（I）とシアン酸エステル化
合物（II）との合計量１００重量部に対し、１５〜６０
重量部、好ましくは２０〜５０重量部である。上記範囲
の下限未満では硬化性が不足し、上限を超えると耐燃性
が低下するため、本発明の目的に適しない。The compounding amount of the cyanate ester compound (II) is 15 to 60 with respect to 100 parts by weight of the total amount of the bismaleimide compound (I) and the cyanate ester compound (II).
Parts by weight, preferably 20 to 50 parts by weight. If it is less than the lower limit of the above range, the curability will be insufficient, and if it exceeds the upper limit, the flame resistance will be reduced, so that it is not suitable for the purpose of the invention.
【０００８】本発明において、無機系難燃剤（III）と
しては、高分子材料に併用し、難燃効果を示す無機物で
あれば、特に限定されるものではない。代表的な無機系
難燃剤としては、水酸化アルミニウム、水酸化マグネシ
ウムなどの水和物、酸化モリブデン、モリブデン酸亜鉛
などのモリブデン化合物、ホウ酸亜鉛、錫酸亜鉛等が挙
げられ、1種もしくは2種以上を適宜混合して使用するこ
とも可能である。より好適なものとしては、水酸化アル
ミニウム、水酸化マグネシウム、水酸化アルミニウムと
モリブデン酸亜鉛、水酸化アルミニウムと錫酸亜鉛が挙
げられる。この内、モリブデン酸亜鉛としては、モリブ
デン酸亜鉛を炭酸カルシウム、酸化亜鉛、タルクに担持
したもの（ケムガード９１１Ａ、Ｂ、Ｃ、シャーウイン
・ウイリアムズ製）が好適である。In the present invention, the inorganic flame retardant (III) is not particularly limited as long as it is an inorganic substance which is used in combination with a polymer material and exhibits a flame retardant effect. Representative inorganic flame retardants include hydrates such as aluminum hydroxide and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, and the like. It is also possible to mix and use more than one kind as appropriate. More preferred are aluminum hydroxide, magnesium hydroxide, aluminum hydroxide and zinc molybdate, and aluminum hydroxide and zinc stannate. Of these, zinc molybdate is preferably a material in which zinc molybdate is supported on calcium carbonate, zinc oxide, or talc (Chemgard 911A, B, C, manufactured by Sherwin Williams).
【０００９】無機系難燃剤（III）の配合量は、ビスマ
レイミド化合物（I）とシアン酸エステル化合物（II）
とエポキシ樹脂（IV）との合計量１００重量部に対し、
３０〜２００重量部、好ましくは５０〜１５０重量部で
ある。上記範囲の下限未満では難燃性向上効果が乏し
く、上限を超えると基材への塗布性やハンダ耐熱性が低
下する。The amounts of the inorganic flame retardant (III) and the bismaleimide compound (I) and the cyanate ester compound (II)
And a total of 100 parts by weight of the epoxy resin (IV),
It is 30 to 200 parts by weight, preferably 50 to 150 parts by weight. If it is less than the lower limit of the above range, the effect of improving the flame retardancy is poor, and if it exceeds the upper limit, the applicability to the substrate and the solder heat resistance are reduced.
【００１０】本発明で使用される非ハロゲン化エポキシ
樹脂（IV）は、1分子中に２個以上のエポキシ基を有す
る非ハロゲン化エポキシ樹脂であれば特に限定されるも
のではない。 代表的な例としては、ビスフェノールＡ
系、ビスフェノールＦ系、フェノールノボラック系、ク
レゾールノボラック系、ビスフェノールＡノボラック
系、多官能フェノール系、ナフタレン系、ビフェニル
系、脂環式系、ポリオール系などのグリシジルエーテ
ル、グリシジルアミン系、グリシジルエステル系、ブタ
ジエンなどの二重結合をエポキシ化した化合物、水酸基
含有シリコン樹脂類とエピクロルヒドリンとの反応によ
り得られる化合物などが挙げられ、1種もしくは2種以上
を適宜混合して使用することも可能である。より好適な
ものとしては、ビスフェノールＦ系、フェノールノボラ
ック系、クレゾールノボラック系、多官能フェノール
系、ナフタレン系のグリシジルエーテルが挙げられる。The non-halogenated epoxy resin (IV) used in the present invention is not particularly limited as long as it is a non-halogenated epoxy resin having two or more epoxy groups in one molecule. A typical example is bisphenol A
Glycidyl ether, glycidylamine-based, glycidyl ester-based, bisphenol F-based, phenol novolak-based, cresol novolak-based, bisphenol A novolak-based, polyfunctional phenol-based, naphthalene-based, biphenyl-based, alicyclic-based, polyol-based, etc. Examples include compounds in which a double bond such as butadiene is epoxidized, compounds obtained by reacting a hydroxyl group-containing silicone resin with epichlorohydrin, and the like. One or more kinds thereof may be used as appropriate. More preferable examples include bisphenol F-based, phenol novolak-based, cresol novolak-based, polyfunctional phenol-based, and naphthalene-based glycidyl ethers.
【００１１】本発明では、必要に応じ、該樹脂組成物の
硬化速度を適宜調節するために硬化促進剤を添加する。
これらは、熱硬化性樹脂の硬化促進剤として一般に使用
されているものであれば、特に限定されない。代表的な
例としては、有機金属塩、イミダゾール類及びその誘導
体並びに第3級アミン類などが挙げられ、1種もしくは2
種以上を適宜混合して使用することも可能である。In the present invention, if necessary, a curing accelerator is added in order to appropriately adjust the curing speed of the resin composition.
These are not particularly limited as long as they are generally used as a curing accelerator for a thermosetting resin. Representative examples include organometallic salts, imidazoles and derivatives thereof, and tertiary amines.
It is also possible to mix and use more than one kind as appropriate.
【００１２】本発明において、所期の特性を損なわない
範囲において、耐燃性の化合物、充填剤などの添加も可
能である。これらは周知であり、一般に使用されている
ものであれば、特に限定はされない。化合物の代表例と
しては、メラミンやベンゾグアナミン変性などの窒素含
有化合物、オキサジン環含有化合物、シリコーン系化合
物などが挙げられる。充填剤の代表的例としては、シリ
カ、マイカ、タルク、ガラス短繊維及び微粉末、中空ガ
ラス等の無機物粉末、シリコーンパウダーなどの有機物
粉末などが挙げられる。In the present invention, a flame-resistant compound, a filler and the like can be added as long as the desired properties are not impaired. These are well known and are not particularly limited as long as they are commonly used. Representative examples of the compound include nitrogen-containing compounds such as melamine and benzoguanamine-modified, oxazine ring-containing compounds, and silicone compounds. Typical examples of the filler include silica, mica, talc, short glass fiber and fine powder, inorganic powder such as hollow glass, and organic powder such as silicone powder.
【００１３】本発明において、必要に応じて有機溶剤を
使用するが、その種類としては、該樹脂組成物と相溶す
るものであれば、特に限定されるものではない。その代
表例としては、アセトン、メチルエチルケトン、メチル
セルソルブ、プロピレングリコールメチルエーテル及び
そのアセテート、トルエン、キシレン、ジメチルホルム
アミドなどが挙げられ、1種もしくは２種以上を適宜混
合して使用することも可能である。基材への含浸性を重
視する場合は、沸点１２０〜２００℃程度の溶剤を併用
することが好適である。In the present invention, an organic solvent is used as required, but the type thereof is not particularly limited as long as it is compatible with the resin composition. Representative examples thereof include acetone, methyl ethyl ketone, methyl cellosolve, propylene glycol methyl ether and its acetate, toluene, xylene, dimethylformamide, and the like, and one or more of them can be used as appropriate. is there. When importance is attached to the impregnation property of the base material, it is preferable to use a solvent having a boiling point of about 120 to 200 ° C. in combination.
【００１４】本発明において、所期の特性を損なわない
範囲において、樹脂組成物に、紫外線吸収剤、酸化防止
剤、光重合開始剤、蛍光増白剤などを添加しても良い。
これらは周知であり、一般に使用される化合物であれ
ば、特に限定はされない。その代表的な例としては、ベ
ンソトリアゾール系などの紫外線吸収剤、ヒンダートフ
ェノール系、スチレン化フェノールなどの酸化防止剤、
チオキサントン系などの光重合開始剤、スチルベン誘導
体などの蛍光増白剤が挙げられるビスマレイミド化合物
（I）、シアン酸エステル化合物（II）、無機系難燃剤
（III）を必須成分とする樹脂組成物を、基材に含浸又
は塗布し、加熱等によりＢステージ化して、本発明のプ
リプレグを製造する。本発明の基材としては、各種の電
気絶縁材料用積層板に用いられている周知のものを使用
することが可能である。その材質の代表的な例として
は、Ｅガラス，Ｄガラス，Ｓガラス、及びＱガラスなど
の無機物繊維、ポリイミド、ポリエステルなどの有機繊
維、及びその混合物などが挙げられる。これらの基材
は、その形状により、織布、不織布、ロービング、チョ
プドストランドマット、サーフェシングマットなどが挙
げられる。材質及び形状は、目的とする成形物の用途や
性能により適宜選択され、必要により単独もしくは、２
種類以上の材質及び形状を選択して使用することも可能
である。基材の厚みについては、特に制限はないが、通
常０.０３〜０.５mm程度を使用する。またシランカップ
リング剤などで表面処理したものや機械的に開繊処理を
施したものは、吸湿耐熱性の面から好適である。基材に
対する樹脂組成物の付着量は、プリプレグの樹脂含有率
（無機系難燃剤を含む）で２０〜９０重量％の範囲であ
る。基材に含浸又は塗布させた後、通常１００〜２００
℃の乾燥機で、１〜３０分加熱し、半硬化（Ｂステージ
化）させる方法などにより、本発明のプリプレグを得
る。In the present invention, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent and the like may be added to the resin composition as long as the desired properties are not impaired.
These are well known and are not particularly limited as long as they are commonly used compounds. Typical examples include ultraviolet absorbers such as benzotriazoles, hindered phenols, antioxidants such as styrenated phenols,
Resin composition containing bismaleimide compound (I), cyanate ester compound (II), and inorganic flame retardant (III) as essential components, including photopolymerization initiators such as thioxanthones, and fluorescent brighteners such as stilbene derivatives Is impregnated or applied to a base material, and B-staged by heating or the like to produce a prepreg of the present invention. As the base material of the present invention, it is possible to use well-known materials used for various types of laminates for electric insulating materials. Representative examples of the material include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide and polyester, and mixtures thereof. Depending on the shape, these base materials include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat and the like. The material and shape are appropriately selected depending on the intended use and performance of the molded product, and may be used alone or as necessary.
It is also possible to select and use more than kinds of materials and shapes. The thickness of the substrate is not particularly limited, but is usually about 0.03 to 0.5 mm. Those subjected to a surface treatment with a silane coupling agent or the like or subjected to a mechanical fiber opening treatment are preferable from the viewpoint of heat resistance to moisture absorption. The amount of the resin composition adhered to the substrate is in the range of 20 to 90% by weight in terms of the resin content of the prepreg (including the inorganic flame retardant). After impregnating or applying to the substrate, usually 100-200
The prepreg of the present invention is obtained by, for example, heating in a dryer at a temperature of 1 ° C. for 1 to 30 minutes and semi-curing (B-stage).
【００１５】本発明の積層板は、前述の本発明のプリプ
レグを用いて積層成形したものである。具体的には本発
明のプリプレグを適宜、１ないし複数枚重ね、所望によ
りその片面もしくは両面に、銅やアルミニウムなどの金
属箔を配置した構成で、積層成形することにより製造す
る。使用される金属箔は、電気絶縁材料用途に用いられ
ているものであれば特に制限はない。The laminate of the present invention is formed by laminating the prepreg of the present invention. Specifically, the prepreg of the present invention is produced by laminating one or more sheets of prepreg of the present invention as appropriate, and by laminating a metal foil such as copper or aluminum on one or both sides thereof as desired. The metal foil to be used is not particularly limited as long as it is used for an electric insulating material.
【００１６】成形条件としては、通常の電気絶縁材料用
積層板及び多層板の手法が適用できる。例えば、多段プ
レス、多段真空プレス、連続成形、オートクレーブ成形
機などを使用し、温度：１５０〜２８０℃、圧力：２〜
１００kg/cm2 ，加熱時間：０.０５〜１０時間の範囲が
一般的である。また、本発明のプリプレグと別途作成し
た内層用の配線板を組み合わせ、積層成形することによ
り、多層板を製造することもできる。As the molding conditions, ordinary methods of a laminated board for an electric insulating material and a multilayer board can be applied. For example, using a multi-stage press, a multi-stage vacuum press, a continuous molding, an autoclave molding machine, etc., temperature: 150 to 280 ° C., pressure: 2 to 2
100 kg / cm 2 , heating time: generally 0.05 to 10 hours. In addition, a multilayer board can also be manufactured by combining the prepreg of the present invention with a wiring board for an inner layer which is separately prepared, and by laminating and molding.
【００１７】[0017]
【実施例】実施例１ ビス（３、５−ジメチルー４−マレイミドフェニル）メ
タン７０重量部、 2,2-ビス(4-シアナトフェニル)プロ
パンのプレポリマー（ＢＴ２０７０、重量平均分子量：
2100、三菱ガス化学製）３０重量部をメチルエチルケト
ンに溶解後、水酸化アルミニウム（CL310, 平均粒子
径：１０μｍ、住友化学製）６０重量部、オクチル酸亜
鉛 ０.０1重量部を混合してワニスを得た。このワニス
をメチルエチルケトンで希釈し、厚さ０.１mmのＥガラ
スクロスに含浸塗工し、１４０℃で５分間加熱乾燥し
て、樹脂含有量（無機系難燃剤を含む、以下同様）４８
重量％のプリプレグを得た。次に、このプリプレグを８
枚重ね、１８μmの電解銅箔を上下に配置し、圧力30kg/
cm、温度２３０℃で、１２０分間プレスを行い、積層板
を得た。得られた銅張積層板の物性測定結果を表１に示
す。EXAMPLE 1 A prepolymer of 70 parts by weight of bis (3,5-dimethyl-4-maleimidophenyl) methane and 2,2-bis (4-cyanatophenyl) propane (BT2070, weight average molecular weight:
After dissolving 30 parts by weight of 2100, manufactured by Mitsubishi Gas Chemical) in methyl ethyl ketone, 60 parts by weight of aluminum hydroxide (CL310, average particle diameter: 10 μm, manufactured by Sumitomo Chemical) and 0.01 part by weight of zinc octylate are mixed to prepare a varnish. Obtained. The varnish was diluted with methyl ethyl ketone, impregnated and coated on an E glass cloth having a thickness of 0.1 mm, and dried by heating at 140 ° C. for 5 minutes to obtain a resin content (including an inorganic flame retardant, the same applies hereinafter) of 48.
% By weight of prepreg was obtained. Next, add this prepreg to 8
Laminated, 18μm electrolytic copper foil placed vertically, pressure 30kg /
Pressing was performed at 230 cm for 120 minutes at a temperature of 230 cm to obtain a laminate. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００１８】実施例２ ビス（３−エチルー５−メチルー４−マレイミドフェニ
ル）メタン５０重量部、2,2-ビス(4-シアナトフェニル)
プロパンのプレポリマー（ＢＴ２０７０）１５重量部、
フェノールノボラックエポキシ樹脂（エピコート154、
エポキシ当量：178、油化シェルエポキシ製）３５重量
部、をメチルエチルケトンに溶解後、水酸化アルミニウ
ム（CL310）１００重量部、水酸化マグネシウム（UB65
0、平均粒子径：１０μｍ、宇部マテリアル製）２０重
量部、オクチル酸亜鉛０.０1重量部を混合してワニスを
得た。このワニスを使用し、実施例1と同様にして、積
層板を得た。得られた銅張積層板の物性測定結果を表１
に示す。Example 2 50 parts by weight of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis (4-cyanatophenyl)
15 parts by weight of a propane prepolymer (BT2070),
Phenol novolak epoxy resin (Epicoat 154,
Epoxy equivalent: 178, 35 parts by weight of Yuka Shell Epoxy) were dissolved in methyl ethyl ketone, and then 100 parts by weight of aluminum hydroxide (CL310) and magnesium hydroxide (UB65) were dissolved.
0, an average particle diameter of 10 μm, 20 parts by weight of Ube Materials) and 0.01 part by weight of zinc octylate were mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of the physical properties of the obtained copper-clad laminate.
Shown in
【００１９】実施例３ ビス（３、５−ジエチルー４−マレイミドフェニル）メ
タン６０重量部、2,2-ビス(4-シアナトフェニル)プロパ
ンのプレポリマー（ＢＴ２０７０）２０重量部、クレゾ
ールノボラックエポキシ樹脂（ＥＳＣＮ220H、エポキシ
当量：212、住友化学製）２０重量部をメチルエチルケ
トンに溶解後、水酸化アルミニウム（CL310）８０重量
部、モリブデン酸亜鉛をタルクに担持したもの（ケムガ
ード911C、モリブデン酸亜鉛の担持：１０重量％、平均
粒子径：１０μｍ、シャーウイン・ウイリアムズ製）１
０重量部、ジメチルベンジルアミン０.０１重量部を混
合してワニスを得た。このワニスを使用し、実施例1と
同様にして、積層板を得た。得られた銅張積層板の物性
測定結果を表１に示す。Example 3 60 parts by weight of bis (3,5-diethyl-4-maleimidophenyl) methane, 20 parts by weight of a prepolymer of 2,2-bis (4-cyanatophenyl) propane (BT2070), cresol novolak epoxy resin 20 parts by weight (ESCN220H, epoxy equivalent: 212, manufactured by Sumitomo Chemical) dissolved in methyl ethyl ketone, and then 80 parts by weight of aluminum hydroxide (CL310) and zinc molybdate supported on talc (Chemgard 911C, zinc molybdate supported: 10% by weight, average particle size: 10 μm, manufactured by Sherwin Williams) 1
A varnish was obtained by mixing 0 parts by weight and 0.01 parts by weight of dimethylbenzylamine. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２０】実施例４ ビス（３、５−ジメチルー４−マレイミドフェニル）メ
タン ５５重量部、クレゾールノボラックとクロルシア
ンから得られるノボラックシアネートのプレポリマー
（ＣT−９０、重量平均分子量：2800、LONZA製）２０重
量部、ビスフェノールＦ型エポキシ樹脂（エピコート40
01P、エポキシ当量：480、油化シェルエポキシ製）１０
重量部、クレゾールノボラックエポキシ樹脂（ＥＳＣＮ
220H）１５重量部をメチルエチルケトンに溶解後、水酸
化アルミニウム（CL310）９０重量部、錫酸亜鉛（ZHS、
平均粒子径：１０μｍ、水沢化学製）１０重量部、2-エ
チル-４-メチルイミダゾール ０.０１重量部を混合して
ワニスを得た。このワニスを使用し、実施例1と同様に
して、積層板を得た。得られた銅張積層板の物性測定結
果を表１に示す。Example 4 Prepolymer of 55 parts by weight of bis (3,5-dimethyl-4-maleimidophenyl) methane, novolak cyanate obtained from cresol novolak and chlorocyan (CT-90, weight average molecular weight: 2800, manufactured by LONZA) 20 parts by weight, bisphenol F type epoxy resin (Epicoat 40
01P, epoxy equivalent: 480, oiled shell epoxy) 10
Parts by weight, cresol novolak epoxy resin (ESCN
220H) After dissolving 15 parts by weight in methyl ethyl ketone, 90 parts by weight of aluminum hydroxide (CL310) and zinc stannate (ZHS,
An average particle diameter of 10 μm, 10 parts by weight of Mizusawa Chemical Co., Ltd.) and 0.01 part by weight of 2-ethyl-4-methylimidazole were mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２１】実施例５ ビス（３−エチルー５−メチルー４−マレイミドフェニ
ル）メタン ６０重量部、2,2-ビス(4-シアナトフェニ
ル)プロパンとノボラックシアネート（PT−３０、LONZA
製）のプレポリマー（配合比１：１、重量平均分子量：
2400）２０重量部、フェノールノボラックエポキシ樹脂
（エピコート154）２０重量部、をキシレンに溶解後、
水酸化アルミニウム（CL310）１２０重量部、ジメチル
ベンジルアミン ０.０１重量部を混合してワニスを得
た。このワニスを使用し、実施例1と同様にして、積層
板を得た。得られた銅張積層板の物性測定結果を表１に
示す。Example 5 Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane 60 parts by weight, 2,2-bis (4-cyanatophenyl) propane and novolak cyanate (PT-30, LONZA)
Prepolymer (compounding ratio 1: 1, weight average molecular weight:
2400) 20 parts by weight and 20 parts by weight of phenol novolak epoxy resin (Epicoat 154) are dissolved in xylene,
A varnish was obtained by mixing 120 parts by weight of aluminum hydroxide (CL310) and 0.01 part by weight of dimethylbenzylamine. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２２】実施例６ ビス（３、５−ジエチルー４−マレイミドフェニル）メ
タン ５０重量部、2,2-ビス(4-シアナトフェニル)プロ
パンのプレポリマー（ＢＴ２０７０） ２５重量部、ビ
スフェノールＦ型エポキシ樹脂（エピコート4001P）１
０重量部、ナフタレン型エポキシ樹脂（エピクロンHP-4
032、エポキシ当量：１５０、大日本インキ製）１５重
量部、メチルエチルケトンに溶解後、水酸化アルミニウ
ム（CL310）７０重量部、錫酸亜鉛（ZHS）１０重量部、
ジメチルベンジルアミン ０.０1重量部を混合してワニ
スを得た。このワニスを使用し、実施例1と同様にし
て、積層板を得た。得られた銅張積層板の物性測定結果
を表１に示す。Example 6 Bis (3,5-diethyl-4-maleimidophenyl) methane 50 parts by weight, 2,2-bis (4-cyanatophenyl) propane prepolymer (BT2070) 25 parts by weight, bisphenol F type epoxy Resin (Epicoat 4001P) 1
0 parts by weight, naphthalene type epoxy resin (Epiclon HP-4
032, epoxy equivalent: 150, manufactured by Dainippon Ink) 15 parts by weight, dissolved in methyl ethyl ketone, 70 parts by weight of aluminum hydroxide (CL310), 10 parts by weight of zinc stannate (ZHS),
A varnish was obtained by mixing 0.01 part by weight of dimethylbenzylamine. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２３】実施例７ ビス（３、５−ジメチルー４−マレイミドフェニル）メ
タン ３５重量部、ビス（３、５−ジエチルー４−マレ
イミドフェニル）メタン ２０重量部、 2,2-ビス(4-シ
アナトフェニル)プロパンのプレポリマー（ＢＴ２０７
０） ２０重量部、フェノールノボラックエポキシ樹脂
（エピコート154）２５重量部をプロピレングリコール
モノメチルエーテルに溶解後、水酸化アルミニウム （C
L310）８０重量部、モリブデン酸亜鉛をタルクに担持し
たもの（ケムガード911C）１０重量部、オクチル酸亜鉛
０.０1重量部を混合してワニスを得た。このワニスを
使用し、実施例1と同様にして、積層板を得た。得られ
た銅張積層板の物性測定結果を表１に示す。Example 7 35 parts by weight of bis (3,5-dimethyl-4-maleimidophenyl) methane, 20 parts by weight of bis (3,5-diethyl-4-maleimidophenyl) methane, 2,2-bis (4-cyanatophenyl) methane Prepolymer of phenyl) propane (BT207
0) 20 parts by weight and 25 parts by weight of phenol novolak epoxy resin (Epicoat 154) were dissolved in propylene glycol monomethyl ether, and then aluminum hydroxide (C
L310) 80 parts by weight, 10 parts by weight of zinc molybdate supported on talc (Chemgard 911C), and 0.01 part by weight of zinc octylate were mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２４】比較例1 ビス（３、５−ジメチルー４−マレイミドフェニル）メ
タン ９０重量部、2,2-ビス(4-シアナトフェニル)プロ
パンのプレポリマー（ＢＴ２０７０） １０重量部、水
酸化アルミニウム（CL310）６０重量部、オクチル酸亜
鉛 ０.０1重量部を混合してワニスを得た。このワニス
を使用し、実施例1と同様にして、積層板を得た。得ら
れた銅張積層板の物性測定結果を表１に示す。Comparative Example 1 90 parts by weight of bis (3,5-dimethyl-4-maleimidophenyl) methane, 10 parts by weight of a prepolymer of 2,2-bis (4-cyanatophenyl) propane (BT2070), aluminum hydroxide ( CL310) 60 parts by weight and zinc octylate 0.01 part by weight were mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２５】比較例2 水酸化アルミを使用しない以外は実施例1と同様に行
い、ワニスを得た。このワニスを使用し、実施例1と同
様にして、積層板を得た。得られた銅張積層板の物性測
定結果を表１に示す。Comparative Example 2 A varnish was obtained in the same manner as in Example 1 except that aluminum hydroxide was not used. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２６】比較例３ ビス（３―エチルー５−メチルー４−マレイミドフェニ
ル）メタン ３０重量部、 2,2-ビス(4-シアナトフェニ
ル)プロパンのプレポリマー（ＢＴ２０７０）７０重量
部をメチルエチルケトンに溶解後、水酸化アルミニウム
（CL310）１００重量部、 オクチル酸亜鉛 ０.０1重量
部を混合してワニスを得た。このワニスを使用し、実施
例1と同様にして、積層板を得た。得られた銅張積層板
の物性測定結果を表１に示す。Comparative Example 3 30 parts by weight of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 70 parts by weight of a prepolymer of 2,2-bis (4-cyanatophenyl) propane (BT2070) were dissolved in methyl ethyl ketone. Thereafter, 100 parts by weight of aluminum hydroxide (CL310) and 0.01 part by weight of zinc octylate were mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２７】比較例４ ビス（３―エチルー５−メチルー４−マレイミドフェニ
ル）メタン ５０重量部、 2,2-ビス(4-シアナトフェニ
ル)プロパンのプレポリマー（ＢＴ２０７０）１５重量
部、ビスフェノールＡ型エポキシ樹脂（エピコート100
1、エポキシ当量：480、油化シェルエポキシ製）３５重
量部をメチルエチルケトンに溶解後、オクチル酸亜鉛
０.０1重量部を混合してワニスを得た。このワニスを使
用し、実施例１と同様にして、積層板を得た。得られた
銅張積層板の物性測定結果を表１に示す。Comparative Example 4 Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane 50 parts by weight, 2,2-bis (4-cyanatophenyl) propane prepolymer (BT2070) 15 parts by weight, bisphenol A type Epoxy resin (Epicoat 100
1, epoxy equivalent: 480, oiled shell epoxy) 35 parts by weight dissolved in methyl ethyl ketone, zinc octylate
0.01 part by weight was mixed to obtain a varnish. Using this varnish, a laminate was obtained in the same manner as in Example 1. Table 1 shows the measurement results of physical properties of the obtained copper-clad laminate.
【００２８】[0028]
【表１】 [Table 1]
【００２９】試験方法：ハンダ耐熱性、銅箔ピール強
度、耐薬品性、ＴｇはＪＩＳ Ｃ６４８１に、耐燃性は
ＵＬ９４ 垂直試験方法による。Test method: Solder heat resistance, copper foil peel strength, chemical resistance, Tg according to JIS C6481, and flame resistance according to UL94 vertical test method.
【００３０】[0030]
【発明の効果】本発明によれば、耐燃性に優れかつ電気
特性や耐熱性の良好なハロゲンフリーの樹脂組成物から
得られた、焼却時にダイオキシン等を発生することの無
い、電気絶縁材料用のプリプレグ、及び積層板が提供さ
れる。According to the present invention, an electric insulating material which is obtained from a halogen-free resin composition having excellent flame resistance and good electric characteristics and heat resistance and which does not generate dioxin or the like when incinerated is used. And a laminate are provided.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ａ ５Ｇ３３３ 63/04 63/04 79/00 79/00 Ｚ Ｈ０１Ｂ 3/00 Ｈ０１Ｂ 3/00 Ａ 3/30 3/30 Ｄ Ｈ 3/40 3/40 Ｐ 17/56 17/56 Ａ Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｎ ６１０Ｍ ６１０Ｌ ６１０Ｒ (72)発明者 中井 孝昌 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京工場内 (72)発明者 永井 憲 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京工場内 Ｆターム(参考） 4F072 AA04 AA05 AA07 AB09 AB28 AD11 AD23 AD28 AE01 AE07 AF02 AF03 AF04 AF28 AG03 AJ04 AK02 AK14 AL13 AL14 4J002 CD00X CD02X CD04X CD05X CD06X CD13X CD15X CD18X CM00W DE076 DE146 DE186 DK006 FD010 FD130 FD136 GF00 GQ01 4J043 PC015 PC016 QC24 RA02 RA70 SA13 SB01 TA67 TA68 TB01 UA121 UA131 UA132 UA141 UA151 UA171 UA261 UA352 UA391 UB011 UB012 UB121 UB281 UB301 VA011 VA041 VA042 VA051 VA081 ZA12 ZA13 ZA41 ZB50 ZB59 5G303 AA08 AB20 BA12 CA03 CA09 CA11 CB01 CB17 CB30 5G305 AA06 AA14 AB01 AB24 AB25 AB26 AB31 AB35 BA18 BA23 BA25 CA15 CA21 CA32 CA51 CC02 CC03 CC14 CD01 CD12 CD13 5G333 AA03 AA05 AB13 AB21 BA03 CA03 CB12 CB13 CC03 DA03 DA04 DA06 DA23 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (Reference) C08L 63/00 C08L 63/00 A 5G333 63/04 63/04 79/00 79/00 Z H01B 3/00 H01B 3 / 00 A 3/30 3/30 DH 3/40 3/40 P 17/56 17/56 A H05K 1/03 610 H05K 1/03 610N 610M 610L 610R (72) Inventor Takamasa Nakai 6 Shinjuku, Katsushika-ku, Tokyo No. 1-1, Mitsubishi Gas Chemical Co., Ltd. Tokyo Plant (72) Inventor Ken Nagai 6-1-1, Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Plant F-term (reference) 4F072 AA04 AA05 AA07 AB09 AB28 AD11 AD23 AD28 AE01 AE07 AF02 AF03 AF04 AF28 AG03 AJ04 AK02 AK14 AL13 AL14 4J002 CD00X CD02X CD04X CD05X CD06X CD13X CD15X CD18X CM00W DE076 DE146 DE186 DK006 FD010 FD130 FD136 GF00 TAQ01 TA01 PC01 030 UA141 UA151 UA171 UA261 UA352 UA391 UB011 UB012 UB121 UB281 UB301 VA011 VA04 1 VA042 VA051 VA081 ZA12 ZA13 ZA41 ZB50 ZB59 5G303 AA08 AB20 BA12 CA03 CA09 CA11 CB01 CB17 CB30 5G305 AA06 AA14 AB01 AB24 AB25 AB26 AB31 AB35 BA18 BA23 BA25 CA15 CA21 CA32 CA51 CC02 CC03 CC13 CD03 ACB13 A0313 CC03 DA03 DA04 DA06 DA23
Claims (10)
す）に示す構造単位を有するビスマレイミド化合物
（I）、1分子中に２個以上のシアナト基を有するシアン
酸エステル化合物（II）、無機系難燃剤（III）を必須
成分として含有し、ビスマレイミド化合物（I）とシア
ン酸エステル化合物（II）の配合割合が、各々４０〜８
５重量部、１５〜６０重量部である樹脂組成物を基材に
含浸または塗布したことを特徴とするプリプレグ。(1) The following formula (1): (R 1 represents hydrogen or an alkyl group, R 2 represents an alkyl group), a bismaleimide compound (I) having a structural unit represented by the following formula, a cyanate compound (II) having two or more cyanato groups in one molecule, An inorganic flame retardant (III) is contained as an essential component, and the compounding ratio of the bismaleimide compound (I) and the cyanate ester compound (II) is 40 to 8 each.
A prepreg, wherein a base material is impregnated or coated with 5 parts by weight, 15 to 60 parts by weight of a resin composition.
る非ハロゲン化エポキシ樹脂（IV）をさらに配合したこ
とを特徴とする請求項１記載のプリプレグ。2. The prepreg according to claim 1, further comprising a non-halogenated epoxy resin (IV) having two or more epoxy groups in one molecule.
（３、５−ジメチルー４−マレイミドフェニル）メタ
ン、ビス（３−エチルー５−メチルー４−マレイミドフ
ェニル）メタン、ビス（３、５−ジエチルー４−マレイ
ミドフェニル）メタン、またはそれらの混合物であるこ
とを特徴とする請求項１記載のプリプレグ。3. The bismaleimide compound (I) is bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4) The prepreg according to claim 1, which is -maleimidophenyl) methane or a mixture thereof.
ナト基の三量化によって形成されるトリアジン環を有す
る重量平均分子量500〜5,000のプレポリマーであること
を特徴とする請求項１記載のプリプレグ。4. The prepreg according to claim 1, wherein the cyanate ester compound (II) is a prepolymer having a triazine ring formed by trimerization of a cyanato group and having a weight average molecular weight of 500 to 5,000.
ニウム、水酸化マグネシウム、またはそれらの混合物で
あることを特徴とする請求項１記載のプリプレグ。5. The prepreg according to claim 1, wherein the inorganic flame retardant (III) is aluminum hydroxide, magnesium hydroxide, or a mixture thereof.
ニウムとモリブデン酸亜鉛の混合物であることを特徴と
する請求項１記載のプリプレグ。6. The prepreg according to claim 1, wherein the inorganic flame retardant (III) is a mixture of aluminum hydroxide and zinc molybdate.
ニウムと錫酸亜鉛の混合物であることを特徴とする請求
項１記載のプリプレグ。7. The prepreg according to claim 1, wherein the inorganic flame retardant (III) is a mixture of aluminum hydroxide and zinc stannate.
マレイミド化合物（I）とシアン酸エステル化合物（I
I）とエポキシ樹脂（IV）との合計量１００重量部に対
し、５０〜１５０重量部であることを特徴とする請求項
１記載のプリプレグ。8. The compounding amount of the inorganic flame retardant (III) is such that the bismaleimide compound (I) and the cyanate ester compound (I
The prepreg according to claim 1, wherein the prepreg is used in an amount of 50 to 150 parts by weight based on 100 parts by weight of the total of I) and the epoxy resin (IV).
スフェノールＦ系、フェノールノボラック系、クレゾー
ルノボラック系、多官能フェノール系、ナフタレン系の
グリシジルエーテル、またはそれらの混合物であること
を特徴とする請求項１記載のプリプレグ。9. The non-halogenated epoxy resin (IV) is a bisphenol F-based, phenol novolak-based, cresol novolak-based, polyfunctional phenol-based, naphthalene-based glycidyl ether, or a mixture thereof. Item 2. The prepreg according to Item 1.
プレグを硬化して得られることを特徴とする電気絶縁材
料の積層板又は金属箔張り積層板。10. A laminate of an electrically insulating material or a laminate with a metal foil, obtained by curing the prepreg according to claim 1. Description:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000113154A JP5105657B2 (en) | 2000-04-14 | 2000-04-14 | Prepreg and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000113154A JP5105657B2 (en) | 2000-04-14 | 2000-04-14 | Prepreg and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001294689A true JP2001294689A (en) | 2001-10-23 |
| JP5105657B2 JP5105657B2 (en) | 2012-12-26 |
Family
ID=18625179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000113154A Expired - Fee Related JP5105657B2 (en) | 2000-04-14 | 2000-04-14 | Prepreg and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5105657B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001302761A (en) * | 2000-04-24 | 2001-10-31 | Dainippon Ink & Chem Inc | Thermosetting resin composition, cured item, prepreg for laminate, and printed circuit substrate |
| JP2003003076A (en) * | 2001-06-22 | 2003-01-08 | Hitachi Chem Co Ltd | Flame-retarded resin composition, prepreg using the same, metal foil-clad laminate and printed board |
| WO2003066956A1 (en) * | 2002-02-05 | 2003-08-14 | Ykk Corporation | Flame-retardant molded article and fabric product |
| JP2007288152A (en) * | 2006-03-23 | 2007-11-01 | Hitachi Chem Co Ltd | Laminate |
| KR100793265B1 (en) | 2006-05-30 | 2008-01-17 | 주식회사 나노코 | BT resine composition and manufacturing method therefor |
| JP2009024056A (en) * | 2007-07-18 | 2009-02-05 | Mitsubishi Gas Chem Co Inc | Prepreg and laminate |
| JP2009132886A (en) * | 2007-10-29 | 2009-06-18 | Mitsubishi Gas Chem Co Inc | Resin composition, and prepreg and laminated board each using the same |
| WO2012083727A1 (en) * | 2010-12-23 | 2012-06-28 | 广东生益科技股份有限公司 | Halogen-free high-tg resin composition and prepreg and laminate fabricated by using the same |
| WO2013008684A1 (en) * | 2011-07-14 | 2013-01-17 | 三菱瓦斯化学株式会社 | Resin composition for printed wiring boards |
| CN103173086A (en) * | 2011-12-23 | 2013-06-26 | 江苏国力电力安装工程有限公司 | Fire-retardant integrally sprayed polymer anti-corrosion lining material for wet desulphurization chimneys of thermal power plants |
| US9775238B2 (en) | 2011-11-07 | 2017-09-26 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, and prepreg and laminate using the same |
| JP2018062570A (en) * | 2016-10-13 | 2018-04-19 | 三菱瓦斯化学株式会社 | Resin composition, resin sheet, printed wiring board, and semiconductor device |
| WO2018155672A1 (en) | 2017-02-27 | 2018-08-30 | 株式会社Adeka | Resin composition for fiber-reinforced plastic, cured product of same, and fiber-reinforced plastic comprising said cured product |
| CN113354814A (en) * | 2021-06-22 | 2021-09-07 | 中国科学院长春应用化学研究所 | Modified cyanate resin and preparation method thereof |
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| US10738144B2 (en) | 2016-12-03 | 2020-08-11 | Soochow University | Flame-retardant bismaleimide resin and preparation method thereof |
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| JPH09328601A (en) * | 1995-12-08 | 1997-12-22 | Mitsui Petrochem Ind Ltd | Thermosetting resin composition, prepreg using the same and laminated sheet |
| JPH1112436A (en) * | 1997-06-23 | 1999-01-19 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing semiconductor and semiconductor device made by using it |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001302761A (en) * | 2000-04-24 | 2001-10-31 | Dainippon Ink & Chem Inc | Thermosetting resin composition, cured item, prepreg for laminate, and printed circuit substrate |
| JP4622036B2 (en) * | 2000-04-24 | 2011-02-02 | Ｄｉｃ株式会社 | Thermosetting resin composition, cured product, prepreg for laminated board, and printed wiring board |
| JP2003003076A (en) * | 2001-06-22 | 2003-01-08 | Hitachi Chem Co Ltd | Flame-retarded resin composition, prepreg using the same, metal foil-clad laminate and printed board |
| WO2003066956A1 (en) * | 2002-02-05 | 2003-08-14 | Ykk Corporation | Flame-retardant molded article and fabric product |
| JP2007288152A (en) * | 2006-03-23 | 2007-11-01 | Hitachi Chem Co Ltd | Laminate |
| KR100793265B1 (en) | 2006-05-30 | 2008-01-17 | 주식회사 나노코 | BT resine composition and manufacturing method therefor |
| JP2009024056A (en) * | 2007-07-18 | 2009-02-05 | Mitsubishi Gas Chem Co Inc | Prepreg and laminate |
| JP2009132886A (en) * | 2007-10-29 | 2009-06-18 | Mitsubishi Gas Chem Co Inc | Resin composition, and prepreg and laminated board each using the same |
| WO2012083727A1 (en) * | 2010-12-23 | 2012-06-28 | 广东生益科技股份有限公司 | Halogen-free high-tg resin composition and prepreg and laminate fabricated by using the same |
| WO2013008684A1 (en) * | 2011-07-14 | 2013-01-17 | 三菱瓦斯化学株式会社 | Resin composition for printed wiring boards |
| JPWO2013008684A1 (en) * | 2011-07-14 | 2015-02-23 | 三菱瓦斯化学株式会社 | Resin composition for printed wiring board |
| US9775238B2 (en) | 2011-11-07 | 2017-09-26 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, and prepreg and laminate using the same |
| CN103173086A (en) * | 2011-12-23 | 2013-06-26 | 江苏国力电力安装工程有限公司 | Fire-retardant integrally sprayed polymer anti-corrosion lining material for wet desulphurization chimneys of thermal power plants |
| JP2018062570A (en) * | 2016-10-13 | 2018-04-19 | 三菱瓦斯化学株式会社 | Resin composition, resin sheet, printed wiring board, and semiconductor device |
| WO2018155672A1 (en) | 2017-02-27 | 2018-08-30 | 株式会社Adeka | Resin composition for fiber-reinforced plastic, cured product of same, and fiber-reinforced plastic comprising said cured product |
| KR20190120173A (en) | 2017-02-27 | 2019-10-23 | 가부시키가이샤 아데카 | Resin composition for fiber reinforced plastics, its hardened | cured material, and the fiber reinforced plastics which consist of the said hardened | cured material |
| US11649319B2 (en) | 2017-02-27 | 2023-05-16 | Adeka Corporation | Resin composition for fiber-reinforced plastic, cured product of same, and fiber-reinforced plastic comprising said cured product |
| CN113354814A (en) * | 2021-06-22 | 2021-09-07 | 中国科学院长春应用化学研究所 | Modified cyanate resin and preparation method thereof |
| CN113354814B (en) * | 2021-06-22 | 2023-05-05 | 中国科学院长春应用化学研究所 | Modified cyanate resin and preparation method thereof |
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