JP2000273291A - Thermosetting resin composition, prepreg and laminate - Google Patents
Thermosetting resin composition, prepreg and laminateInfo
- Publication number
- JP2000273291A JP2000273291A JP11078683A JP7868399A JP2000273291A JP 2000273291 A JP2000273291 A JP 2000273291A JP 11078683 A JP11078683 A JP 11078683A JP 7868399 A JP7868399 A JP 7868399A JP 2000273291 A JP2000273291 A JP 2000273291A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- prepared
- laminate
- thermosetting resin
- benzoxazine ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱硬化性樹脂組成
物、プリプレグ及び積層板に関する。[0001] The present invention relates to a thermosetting resin composition, a prepreg, and a laminate.
【０００２】[0002]
【従来の技術】積層板（本発明において積層板には片面
又は両面を金属はくで覆った積層板、すなわち金属張積
層板を含む）は、次のようにして作製される。まず、熱
硬化性樹脂、硬化剤など必要な材料を加えてワニスを調
製し、このワニスを繊維基材に含浸乾燥してプリプレグ
を作製する。次に、このプリプレグを所定枚数重ねて加
熱加圧して積層板を作製する。このとき、プリプレグの
片面又は両面に金属はくを重ねて加熱加圧すると金属張
積層板となる。2. Description of the Related Art A laminated board (a laminated board in which one or both surfaces are covered with a metal foil in the present invention, that is, a metal-clad laminate is included) is manufactured as follows. First, a varnish is prepared by adding necessary materials such as a thermosetting resin and a curing agent, and the varnish is impregnated into a fiber base and dried to prepare a prepreg. Next, a predetermined number of the prepregs are stacked and heated and pressed to produce a laminate. At this time, when a metal foil is overlaid on one or both surfaces of the prepreg and heated and pressed, a metal-clad laminate is obtained.
【０００３】積層板、特に金属張積層板の主要な用途
は、プリント配線板である。このため積層板には、プリ
ント配線板に加工するときの加工性、特に穴あけ加工性
が良好であること、部品をはんだリフローなどにより実
装するとき高温度にさらされることからはんだ耐熱性が
良好であること、高温環境下でも変形劣化しないように
必要なガラス転移温度（以下Ｔｇとする）を有している
こと、耐燃性が良好であることなどが求められる。A major use of laminates, especially metal-clad laminates, is for printed wiring boards. For this reason, the laminate has good workability when processing into a printed wiring board, particularly good drilling workability, and has good solder heat resistance because it is exposed to high temperatures when components are mounted by solder reflow. It is required to have a certain glass transition temperature (hereinafter referred to as Tg) so as not to be deformed and deteriorated even in a high temperature environment, and to have good flame resistance.
【０００４】構造中にベンゾオキサジン環を有する樹脂
は、硬化物のＴｇが高いことが知られており（特開平７
−１８８３６４号公報参照）、構造中にベンゾオキサジ
ン環を有する樹脂を必須成分とする熱硬化性樹脂組成物
を用いて積層板を製造する試みがなされてきた。It is known that a resin having a benzoxazine ring in its structure has a high Tg of a cured product (Japanese Patent Laid-Open No.
JP-A-188364), and an attempt has been made to produce a laminate using a thermosetting resin composition containing a resin having a benzoxazine ring in the structure as an essential component.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、構造中
にベンゾオキサジン環を有する樹脂は、硬化物の化学構
造の骨格がリジットとなるため、構造中にベンゾオキサ
ジン環を有する樹脂を必須成分とする熱硬化性樹脂組成
物を用いて製造された積層板は、スルーホール接続用の
穴あけ加工時に層間クラックが発生し易いという欠点が
あった。However, in a resin having a benzoxazine ring in the structure, a resin having a benzoxazine ring in the structure is an essential component because the skeleton of the chemical structure of the cured product is rigid. The laminate manufactured using the curable resin composition has a disadvantage that interlayer cracks are easily generated during drilling for connecting through holes.
【０００６】本発明は係る状況に鑑みなされたもので、
請求項１又は２に記載の発明は、構造中にベンゾオキサ
ジン環を有する樹脂を必須成分とする熱硬化性樹脂組成
物を用いて積層板としたときの穴あけ加工時に層間クラ
ック発生の少ない熱硬化性樹脂組成物を提供することを
目的とする。The present invention has been made in view of the above circumstances,
The invention according to claim 1 or 2 is a thermosetting resin which is less likely to cause interlayer cracking when a laminate is formed by using a thermosetting resin composition containing a resin having a benzoxazine ring in the structure as an essential component. It is intended to provide a conductive resin composition.
【０００７】また、請求項３に記載の発明は、構造中に
ベンゾオキサジン環を有する樹脂を必須成分とする熱硬
化性樹脂組成物を用いて積層板としたときの穴あけ加工
時に層間クラック発生の少ないプリプレグを提供するこ
とを目的とする。[0007] Further, the invention according to claim 3 is to prevent the occurrence of interlayer cracks during drilling when a laminate is formed using a thermosetting resin composition containing a resin having a benzoxazine ring in the structure as an essential component. The purpose is to provide less prepreg.
【０００８】さらに、請求項４に記載の発明は、構造中
にベンゾオキサジン環を有する樹脂を必須成分とする熱
硬化性樹脂組成物を用いた積層板であって、穴あけ加工
時に層間クラック発生の少ない積層板を提供することを
目的とする。Further, the invention according to claim 4 is a laminate using a thermosetting resin composition containing a resin having a benzoxazine ring in the structure as an essential component, wherein interlayer cracks are generated during drilling. An object is to provide a small number of laminates.
【０００９】[0009]
【課題を解決するための手段】請求項１に記載の発明
は、構造中にベンゾオキサジン環を有する樹脂及びゴム
を必須成分として含む熱硬化性樹脂組成物である。The invention described in claim 1 is a thermosetting resin composition containing a resin having a benzoxazine ring in its structure and a rubber as essential components.
【００１０】構造中にベンゾオキサジン環を有する樹脂
にゴムを配合することによるＴｇの低下を小さくできる
ことから、ゴムとしてはアクリロニトリル−ブタジエン
共重合体を用いるのが好ましい。すなわち、請求項２に
記載の発明は、ゴムがアクリロニトリル−ブタジエン共
重合体である請求項１に記載の熱硬化性樹脂組成物であ
る。It is preferable to use an acrylonitrile-butadiene copolymer as the rubber because the reduction in Tg caused by blending the rubber with the resin having a benzoxazine ring in the structure can be reduced. That is, the invention according to claim 2 is the thermosetting resin composition according to claim 1, wherein the rubber is an acrylonitrile-butadiene copolymer.
【００１１】また、請求項３に記載の発明は、請求項１
に記載の熱硬化性樹脂組成物をワニスとして繊維基材に
含浸乾燥してなるプリプレグである。[0011] The invention according to claim 3 is based on claim 1.
A prepreg obtained by impregnating and drying a thermosetting resin composition described in 1 above as a varnish on a fiber base material.
【００１２】さらに請求項４に記載の発明は、請求項２
に記載のプリプレグを加熱加圧してなる積層板である。Further, the invention according to claim 4 is the invention according to claim 2.
A laminate obtained by heating and pressurizing the prepreg described in 1. above.
【００１３】[0013]
【発明の実施の形態】ベンゾオキサジン環は化１の
（１）に示すような構造を有している。BEST MODE FOR CARRYING OUT THE INVENTION The benzoxazine ring has a structure as shown in Chemical formula 1 (1).
【化１】 （ただし、化１の（１）中のＲ１はアルキル基、シクロ
ヘキシル基、フェニル基又はアルキル基若しくはアルコ
キシル基で置換された置換フェニル基である。）Embedded image (However, R 1 in formula (1) is an alkyl group, a cyclohexyl group, a phenyl group, or a substituted phenyl group substituted with an alkyl group or an alkoxyl group.)
【００１４】ベンゾオキサジン環は加熱により構造中の
酸素原子がベンゼン核に結合した水酸基すなわちフェノ
ール性水酸基を生成しながら開環し、１分子中に２以上
のベンゾオキサジン環を有するときには三次元網目状に
重合して硬化する。また、１分子中ベンゾオキサジン環
を１個有する樹脂であっても、例えばエポキシ樹脂のよ
うにフェノール性水酸基と反応性を有する官能基を有す
る樹脂を加えておくことによって三次元網目状に硬化さ
せることができる。この反応は、反応に伴う副生成物が
ないため、硬化物中にボイドのような欠陥を生じにくい
という利点がある。A benzoxazine ring is opened by heating to form a hydroxyl group bonded to a benzene nucleus, that is, a phenolic hydroxyl group, when an oxygen atom in the structure is opened. When one molecule has two or more benzoxazine rings, a three-dimensional network is formed. Polymerizes and cures. Even a resin having one benzoxazine ring in one molecule is cured into a three-dimensional network by adding a resin having a functional group reactive with a phenolic hydroxyl group such as an epoxy resin. be able to. This reaction has the advantage that defects such as voids hardly occur in the cured product because there are no by-products accompanying the reaction.
【００１５】構造中にベンゾオキサジン環を有する樹脂
は、フェノール性水酸基を有する化合物に１級アミン及
びホルムアルデヒドを反応させることによって合成する
ことができる（特開昭４９−４７３７８号公報参照）。A resin having a benzoxazine ring in the structure can be synthesized by reacting a compound having a phenolic hydroxyl group with a primary amine and formaldehyde (see JP-A-49-47378).
【００１６】構造中にベンゾオキサジン環を有する樹脂
の合成に使用されるフェノール性水酸基を有する化合物
としては、フェノール類を使用することができ、特に制
限はない。As the compound having a phenolic hydroxyl group used in the synthesis of a resin having a benzoxazine ring in the structure, phenols can be used, and there is no particular limitation.
【００１７】１分子中に２以上のフェノール性水酸基を
有するフェノール類を用いることにより、１分子中に２
以上のベンゾオキサジン環を有する樹脂を合成すること
ができる。１分子中に２以上のフェノール性水酸基を有
するフェノール類としては、カテコール、ヒドロキノ
ン、レゾルシノール、ビスフェノールＡ、ビスフェノー
ルＦおよびその位置異性体、ビスフェノールＳ、テトラ
フルオロビスフェノールＡ、レゾール樹脂、フェノール
ノボラック樹脂、フェノール変性キシレン樹脂、アルキ
ルフェノール樹脂、メラミンフェノール樹脂、ベンゾグ
アナミンフェノール樹脂、フェノール変性ポリブタジエ
ンなどが挙げられる。なかでも、フェノールノボラック
樹脂を用いると架橋密度と度が大となり、Ｔｇが高くな
ることから好ましい。By using a phenol having two or more phenolic hydroxyl groups in one molecule, two or more phenolic hydroxyl groups can be used in one molecule.
A resin having the above benzoxazine ring can be synthesized. Examples of phenols having two or more phenolic hydroxyl groups in one molecule include catechol, hydroquinone, resorcinol, bisphenol A, bisphenol F and its positional isomers, bisphenol S, tetrafluorobisphenol A, resole resin, phenol novolak resin, phenol Modified xylene resin, alkyl phenol resin, melamine phenol resin, benzoguanamine phenol resin, phenol-modified polybutadiene and the like can be mentioned. Among them, the use of a phenol novolak resin is preferable because the crosslink density and degree are increased and Tg is increased.
【００１８】構造中にベンゾオキサジン環を有する樹脂
の合成に使用される１級アミンとしては、アルキルアミ
ン、シクロヘキシルアミン、アニリン、アルキル基若し
くはアルコキシル基で置換された置換アニリンが挙げら
れる。The primary amine used in the synthesis of the resin having a benzoxazine ring in the structure includes alkylamine, cyclohexylamine, aniline, and substituted aniline substituted with an alkyl group or an alkoxyl group.
【００１９】構造中にベンゾオキサジン環を有する樹脂
は、フェノール類と１級アミンとを混合しておき、７０
℃以上に加熱したホルムアルデヒド中に添加して、７０
〜１１０℃で反応させ、その後水分を除去することによ
り調製することができる。The resin having a benzoxazine ring in the structure is prepared by mixing a phenol and a primary amine,
Into formaldehyde heated to at least
It can be prepared by reacting at ~ 110 ° C and then removing water.
【００２０】例えば、耐燃性を補完するかめに臭素化エ
ポキシ樹脂を併用するなど、構造中にベンゾオキサジン
環を有する樹脂と他の熱硬化性樹脂を併用することもで
きる。併用する熱硬化性樹脂としては、ベンゾオキサジ
ン環の開環により生成するフェノール性水酸基と反応す
ることからエポキシ樹脂が好ましい。エポキシ樹脂とし
ては、特に制限はなく、公知のエポキシ樹脂を併用する
ことができる。このようなエポキシ樹脂としては、ビス
フェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポ
キシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、フェノ
ールノボラック型エポキシ樹脂、クレゾールノボラック
型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエス
テル型エポキシ樹脂、グリシジルアミン型エポキシ樹
脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型
エポキシ樹脂、これらのハロゲン化物、水素添加物など
が挙げられる。これらのエポキシ樹脂は、単独で用いて
もよく、また、二種類以上を組み合わせて用いてもよ
い。また、エポキシ樹脂の硬化を確実にするため、フェ
ノールノボラック樹脂をエポキシ樹脂と共に併用するの
が好ましい。この場合、併用するフェノールノボラック
樹脂の配合量はベンゾオキサジン環を有する樹脂と併用
されるエポキシ樹脂のエポキシ当量や配合量によって異
なり、その都度最適な配合量を定める必要がある。For example, a resin having a benzoxazine ring in the structure and another thermosetting resin can be used in combination, for example, a brominated epoxy resin is used in combination to complement the flame resistance. As the thermosetting resin to be used in combination, an epoxy resin is preferable because it reacts with a phenolic hydroxyl group generated by opening of the benzoxazine ring. The epoxy resin is not particularly limited, and a known epoxy resin can be used in combination. Such epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, Glycidylamine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, halides and hydrogenated products thereof, and the like can be given. These epoxy resins may be used alone or in combination of two or more. In order to ensure the curing of the epoxy resin, it is preferable to use a phenol novolak resin together with the epoxy resin. In this case, the amount of the phenol novolak resin used in combination differs depending on the epoxy equivalent and the amount of the epoxy resin used in combination with the resin having a benzoxazine ring, and it is necessary to determine the optimum amount each time.
【００２１】構造中にベンゾオキサジン環を有する樹脂
と他の熱硬化性樹脂を併用する場合、構造中にベンゾオ
キサジン環を有する樹脂の特性を活かすためには、熱硬
化性樹脂全体の１／２を超えない範囲で併用するのが好
ましく、２／５を超えない範囲で併用するのがより好ま
しい。When a resin having a benzoxazine ring in the structure is used in combination with another thermosetting resin, in order to take advantage of the properties of the resin having a benzoxazine ring in the structure, one-half of the entire thermosetting resin must be used. Is preferably used together within a range not exceeding, and more preferably within a range not exceeding ／.
【００２２】本発明において必須成分として配合される
ゴムとしては、ポリウレタン系、アクリル系、ポリエス
テル系、ポリアミド系、酢酸ビニル系、ブタジエン系、
アクリロニトリル−ブタジエン共重合体系などの各種合
成ゴムが挙げられる。なかでも、アクリロニトリル−ブ
タジエン共重合体は配合したときのＴｇの低下を小さく
抑えることができて好ましい。The rubber compounded as an essential component in the present invention includes polyurethane, acrylic, polyester, polyamide, vinyl acetate, butadiene, and the like.
Various synthetic rubbers such as an acrylonitrile-butadiene copolymer system are exemplified. Among them, the acrylonitrile-butadiene copolymer is preferable because it can suppress a decrease in Tg when blended.
【００２３】ゴムの配合量は、熱硬化性樹脂の全量１０
０重量部に対して０．５〜４０重量部とするのが好まし
く、１〜３５重量部とするのがより好ましい。ゴムの配
合量が０．５重量部未満であると層間クラック発生を抑
えられなくなる傾向に有り、４０重量部を超えると、Ｔ
ｇが小さくなる傾向にある。The compounding amount of the rubber is 10% of the total amount of the thermosetting resin.
It is preferably 0.5 to 40 parts by weight, more preferably 1 to 35 parts by weight, based on 0 parts by weight. If the amount of the rubber is less than 0.5 part by weight, the occurrence of interlayer cracks tends to be unable to be suppressed.
g tends to be small.
【００２４】本発明の熱硬化性樹脂組成物は、ワニスと
してプリプレグを作製に供される。ワニスとするときに
用いられる溶剤としては、アセトン、メチルエチルケト
ン、トルエン、キシレン、４−メチル−２−ペンタノ
ン、酢酸エチル、エチレングリコールモノエチルエーテ
ル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチル
アセトアミド、エタノールなどが挙げられる。これらの
溶剤は、単独で用いてもよく、２種類以上を組み合わせ
て用いてもよい。The thermosetting resin composition of the present invention is used for preparing a prepreg as a varnish. Solvents used when preparing varnish include acetone, methyl ethyl ketone, toluene, xylene, 4-methyl-2-pentanone, ethyl acetate, ethylene glycol monoethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, Ethanol and the like can be mentioned. These solvents may be used alone or in combination of two or more.
【００２５】ワニスを繊維基材に含浸乾燥してプリプレ
グを作製するが、使用される繊維基材としては、ガラス
織布、ガラス不織布、紙、アラミド繊維織布など公知の
繊維基材を使用することができ、特に制限はない。ま
た、ワニスを含浸乾燥する工程についても特に制限はな
い。A prepreg is prepared by impregnating and drying a varnish into a fiber base material. As the fiber base material to be used, a known fiber base material such as glass woven fabric, glass nonwoven fabric, paper, and aramid fiber woven fabric is used. There are no special restrictions. There is no particular limitation on the step of impregnating and drying the varnish.
【００２６】このようにして製造されたプリプレグを、
製造しようとする積層板の厚さに応じて必要な枚数重ね
て加熱加圧して積層板を製造する。積層板を製造する工
程については特に制限はなく、従来公知の方法によるこ
とができる。なお、銅張積層板は、プリプレグの片側又
は両側に銅はくを配置しておくことにより製造される。The prepreg thus produced is
A required number of sheets are laminated according to the thickness of the laminate to be manufactured and heated and pressed to produce a laminate. There is no particular limitation on the step of manufacturing the laminate, and a conventionally known method can be used. The copper clad laminate is manufactured by arranging a copper foil on one or both sides of a prepreg.
【００２７】[0027]
【実施例】フェノールノボラック樹脂の合成 フェノール１．９重量部、ホルマリン（３７重量％水溶
液）１．１５重量部、及びしゅう酸０．００４重量部を
フラスコに仕込み、還流温度で６時間反応させてフェノ
ールノボラック樹脂を合成した。引き続き、フラスコ内
部の圧力が６６６６．１Ｐａを超えないように減圧して
未反応のフェノール及び水を留去した。EXAMPLE Synthesis of phenol novolak resin 1.9 parts by weight of phenol, 1.15 parts by weight of formalin (37% by weight aqueous solution), and 0.004 parts by weight of oxalic acid were charged into a flask and reacted at reflux temperature for 6 hours. A phenol novolak resin was synthesized. Subsequently, the pressure inside the flask was reduced so as not to exceed 6666.1 Pa, and unreacted phenol and water were distilled off.
【００２８】構造中にベンゾオキサジン環を有する樹脂
の合成 得られたフェノールノボラック樹脂１．７重量部をアニ
リン１．４９重量部中に投入し８０℃に保持して５時間
撹拌してフェノールノボラック樹脂とアニリンとの混合
液を調製した。フラスコに、ホルマリン（３７重量％水
溶液）１．１５重量部を仕込み、９０℃に加熱した。そ
の中に調製したフェノールノボラック樹脂とアニリンと
の混合液を３０分間かけて少しずつ投入した。投入終了
後３０分間還流温度に保ち、その後温度を１００℃にし
て２時間反応させて構造中にベンゾオキサジン環を有す
る樹脂を合成した。引き続き、フラスコ内部の圧力が６
６６６．１Ｐａを超えないように減圧して縮合水を留去
した。Synthesis of a resin having a benzoxazine ring in the structure 1.7 parts by weight of the obtained phenol novolak resin was placed in 1.49 parts by weight of aniline, kept at 80 ° C., stirred for 5 hours, and stirred. And a mixture of aniline was prepared. The flask was charged with 1.15 parts by weight of formalin (37% by weight aqueous solution) and heated to 90 ° C. The prepared mixture of phenol novolak resin and aniline was gradually added thereto over 30 minutes. After maintaining the reflux temperature for 30 minutes after the completion of the charging, the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours to synthesize a resin having a benzoxazine ring in the structure. Subsequently, the pressure inside the flask was increased to 6
The condensation water was distilled off under reduced pressure so as not to exceed 666.1 Pa.
【００２９】実施例１ 前記で合成したフェノールノボラック樹脂２０重量部、
前記で合成した構造中にベンゾオキサジン環を有する樹
脂８０重量部、臭素化エポキシ樹脂（エポキシ当量４０
０ｇ／ｅｑ、臭素含有量４８重量％、東都化成株式会社
製、ＹＤＢ−４００（商品名）を使用）２５重量部及び
粒子径７０μｍのカルボキシル基変性架橋アクリロニト
リル−ブタジエン共重合体（アクリロニトリル含有量２
０．０モル％、ＪＳＲ株式会社製、ＸＥＲ−９１（商品
名）を使用）１．２５重量部をメチルエチルケトンに、
不揮発分が７０重量％となるように溶解させることによ
りワニスを調製した。調製したワニスを厚さ０．２ｍｍ
のガラスクロス（日東紡績株式会社製）に含浸し、温度
１６０℃で４分間乾燥することによりプリプレグを作製
した。作製したプリプレグ８枚を重ね、その両面に厚さ
１８μｍの銅はくを重ね、温度１８５℃、圧力４ＭＰａ
で１００分間加熱加圧することにより厚さ１．５ｍｍの
両面銅張積層板を作製した。Example 1 20 parts by weight of the phenol novolak resin synthesized above,
80 parts by weight of a resin having a benzoxazine ring in the structure synthesized above, and a brominated epoxy resin (epoxy equivalent 40
0 g / eq, bromine content 48% by weight, manufactured by Toto Kasei Co., Ltd., using YDB-400 (trade name)) 25 parts by weight and a carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer (acrylonitrile content 2 having a particle diameter of 70 μm)
0.0 mol%, manufactured by JSR Corporation, using XER-91 (trade name)) 1.25 parts by weight to methyl ethyl ketone,
A varnish was prepared by dissolving the nonvolatile matter so as to be 70% by weight. 0.2 mm thick varnish prepared
Was impregnated into a glass cloth (manufactured by Nitto Boseki Co., Ltd.) and dried at a temperature of 160 ° C. for 4 minutes to prepare a prepreg. Eight sheets of the prepared prepreg are stacked, and copper foil having a thickness of 18 μm is stacked on both surfaces thereof, at a temperature of 185 ° C. and a pressure of 4 MPa.
For 100 minutes to produce a 1.5 mm-thick double-sided copper-clad laminate.
【００３０】実施例２ カルボキシル基変性架橋アクリロニトリル−ブタジエン
共重合体の配合量を６．２５重量部に変更したほかは実
施例１と同様にしてワニスを調製し、プリプレグを作製
し、両面銅張積層板を作製した。Example 2 A varnish was prepared in the same manner as in Example 1 except that the amount of the carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer was changed to 6.25 parts by weight, and a prepreg was prepared. A laminate was prepared.
【００３１】実施例３ カルボキシル基変性架橋アクリロニトリル−ブタジエン
共重合体の配合量を１２．５重量部に変更したほかは実
施例１と同様にしてワニスを調製し、プリプレグを作製
し、両面銅張積層板を作製した。Example 3 A varnish was prepared in the same manner as in Example 1 except that the amount of the carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer was changed to 12.5 parts by weight, and a prepreg was prepared. A laminate was prepared.
【００３２】実施例４ カルボキシル基変性架橋アクリロニトリル−ブタジエン
共重合体の配合量を３１．２５重量部に変更したほかは
実施例１と同様にしてワニスを調製し、プリプレグを作
製し、両面銅張積層板を作製した。Example 4 A varnish was prepared in the same manner as in Example 1 except that the amount of the carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer was changed to 31.25 parts by weight, and a prepreg was prepared. A laminate was prepared.
【００３３】実施例５ カルボキシル基変性架橋アクリロニトリル−ブタジエン
共重合体をエポキシ化ポリブタジエン（エポキシ当量２
００ｇ／ｅｑ、出光アトケム株式会社製、デナレックス
Ｒ−４５ＥＰＩ（商品名）を使用）に変更し、配合量を
１．２５重量部としたほかは実施例１と同様にしてワニ
スを調製し、プリプレグを作製し、両面銅張積層板を作
製した。Example 5 A carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer was converted to an epoxidized polybutadiene (epoxy equivalent 2
A varnish was prepared in the same manner as in Example 1 except that the varnish was changed to 00g / eq, using Denarex R-45EPI (trade name) manufactured by Idemitsu Atchem Co., Ltd., and the blending amount was changed to 1.25 parts by weight. And a double-sided copper-clad laminate was prepared.
【００３４】実施例６ エポキシ化ポリブタジエンの配合量を６．２５重量部に
変更したほかは実施例１と同様にしてワニスを調製し、
プリプレグを作製し、両面銅張積層板を作製した。Example 6 A varnish was prepared in the same manner as in Example 1 except that the amount of the epoxidized polybutadiene was changed to 6.25 parts by weight.
A prepreg was prepared, and a double-sided copper-clad laminate was prepared.
【００３５】実施例７ エポキシ化ポリブタジエンの配合量を１２．５重量部に
変更したほかは実施例１と同様にしてワニスを調製し、
プリプレグを作製し、両面銅張積層板を作製した。Example 7 A varnish was prepared in the same manner as in Example 1 except that the amount of the epoxidized polybutadiene was changed to 12.5 parts by weight.
A prepreg was prepared, and a double-sided copper-clad laminate was prepared.
【００３６】実施例８ エポキシ化ポリブタジエンの配合量を３１．２５重量部
に変更したほかは実施例１と同様にしてワニスを調製
し、プリプレグを作製し、両面銅張積層板を作製した。Example 8 A varnish was prepared in the same manner as in Example 1 except that the amount of the epoxidized polybutadiene was changed to 31.25 parts by weight, a prepreg was prepared, and a double-sided copper-clad laminate was prepared.
【００３７】比較例 カルボキシル基変性架橋アクリロニトリル−ブタジエン
共重合体を配合せず、そのほかは実施例１と同様にして
ワニスを調製し、プリプレグを作製し、両面銅張積層板
を作製した。Comparative Example A varnish was prepared in the same manner as in Example 1 except that the carboxyl group-modified crosslinked acrylonitrile-butadiene copolymer was not blended, a prepreg was prepared, and a double-sided copper-clad laminate was prepared.
【００３８】以上で作製した両面銅張積層板についてス
ルーホール加工時に発生する層間クラックの発生の有
無、耐熱性、耐湿耐熱性を調べた。その結果を表１に示
す。With respect to the double-sided copper-clad laminate prepared as described above, the presence or absence of interlayer cracks generated during through-hole processing, heat resistance, and moisture resistance were examined. Table 1 shows the results.
【００３９】試験方法は以下の通りとした。 層間クラックの発生数：作製した両面銅張積層板を２枚
重ねにし、回転速度７０ｋｒｐｍ、送り速度２．１ｍ／
分のドリル加工条件で０．４ｍｍの穴あけ加工を行い、
この穴に無電解めっきを施した。そして、穴の断面を顕
微鏡で観察することにより層間クラックの発生の有無を
調べた。１００穴について観察して層間クラックが発生
した穴数を示す。 耐燃性：ＵＬ−９４に準拠して調べた。 耐湿耐熱性：片面の銅はくを全面エッチング除去し、他
の片面は半分だけ銅はくをエッチング除去した、５０ｍ
ｍ×５０ｍｍの試験片を用意し、温度１２１℃、圧力２
１３０ｈＰａのプレッシャークッカー処理装置内に６時
間保持した。この試験片を２６０℃に加熱されたはんだ
槽に３０秒間沈め、ふくれ及びミーズリングの発生の有
無を目視観察した。表１において各記号は、○：変化な
し、△：ミーズリング又は目浮き発生、×：ふくれ発生
を意味する。 ガラス転移温度（Ｔｇ）：ＪＩＳ Ｃ ６４８１に定め
るＴＭＡ法に従って熱分析装置（デュポン社製）を使用
して測定した。The test method was as follows. Number of occurrences of interlayer cracks: Two double-sided copper-clad laminates were stacked, and the rotation speed was 70 krpm and the feed speed was 2.1 m /
Drilling 0.4mm under the drilling condition of
This hole was subjected to electroless plating. Then, the presence or absence of interlayer cracks was examined by observing the cross section of the hole with a microscope. The number of holes where interlayer cracks occur is shown by observing 100 holes. Flame resistance: Investigated in accordance with UL-94. Moisture and heat resistance: 50 m in which copper foil on one side is etched away and copper foil on the other side is etched off only half.
Prepare a test piece of mx 50 mm, temperature 121 ° C, pressure 2
The pressure cooker was kept at 130 hPa for 6 hours. The test piece was immersed in a solder bath heated to 260 ° C. for 30 seconds, and the occurrence of blistering and measling was visually observed. In Table 1, each symbol represents ○: no change, Δ: occurrence of measling or bleeding, ×: occurrence of blistering. Glass transition temperature (Tg): Measured using a thermal analyzer (manufactured by DuPont) according to the TMA method specified in JIS C6481.
【００４０】[0040]
【表１】 [Table 1]
【００４１】表１から、ゴムを配合した実施例１〜８で
は、層間クラックの発生が認められなくなっているこ
と、耐燃性はゴムを配合したことによる影響がないこ
と、耐湿耐熱性はゴムを配合しない比較例と同等ないし
やや劣る程度であること、ゴムとしてアクリロニトリル
−ブタジエン共重合体を配合した実施例１〜４は、エポ
キシ化ポリブタジエンを配合した実施例５〜８と比較し
てＴｇの低下が小さいことが示される。It can be seen from Table 1 that in Examples 1 to 8 in which rubber was blended, the occurrence of interlayer cracks was no longer observed, that the flame resistance was not affected by the rubber being blended, and that the moisture and heat resistance was that rubber was used. Examples 1-4 in which the acrylonitrile-butadiene copolymer was blended as the rubber were lower than those in Examples 5-8 in which the acrylonitrile-butadiene copolymer was blended, as compared with the acrylonitrile-butadiene copolymer as the rubber. Is small.
【００４２】[0042]
【発明の効果】本発明の熱硬化性樹脂組成物を用いて作
製した積層板は、スルーホール加工時に層間クラックの
発生を少なくできる。According to the laminate prepared using the thermosetting resin composition of the present invention, the generation of interlayer cracks during through-hole processing can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 垣谷 稔 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館工場内 Ｆターム(参考） 4F072 AA02 AA04 AA07 AB03 AB06 AB09 AD02 AD11 AG03 AH02 AH31 AJ04 AK05 AL13 4J002 AC032 AC072 BF022 BG002 CC031 CE001 CF002 CK022 CL002 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Minoru Kakitani 1500 Oji Ogawa, Shimodate City, Ibaraki Prefecture F-term in Shimodate Plant, Hitachi Chemical Co., Ltd. 4F072 AA02 AA04 AA07 AB03 AB06 AB09 AD02 AD11 AG03 AH02 AH31 AJ04 AK05 AL13 4J002 AC032 AC072 BF022 BG002 CC031 CE001 CF002 CK022 CL002
Claims (4)
脂及びゴムを必須成分として含む熱硬化性樹脂組成物。1. A thermosetting resin composition comprising a resin having a benzoxazine ring in its structure and a rubber as essential components.
重合体である請求項１に記載の熱硬化性樹脂組成物。2. The thermosetting resin composition according to claim 1, wherein the rubber is an acrylonitrile-butadiene copolymer.
成物をワニスとして繊維基材に含浸乾燥してなるプリプ
レグ。3. A prepreg obtained by impregnating and drying a thermosetting resin composition according to claim 1 or 2 as a varnish on a fiber base material.
してなる積層板。4. A laminate obtained by heating and pressing the prepreg according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11078683A JP2000273291A (en) | 1999-03-23 | 1999-03-23 | Thermosetting resin composition, prepreg and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11078683A JP2000273291A (en) | 1999-03-23 | 1999-03-23 | Thermosetting resin composition, prepreg and laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000273291A true JP2000273291A (en) | 2000-10-03 |
Family
ID=13668681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11078683A Pending JP2000273291A (en) | 1999-03-23 | 1999-03-23 | Thermosetting resin composition, prepreg and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000273291A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005000955A1 (en) * | 2003-06-27 | 2005-01-06 | Henkel Corporation | Heat curable compositions comprising a benzoxazine component and an acrylonitrile-butadiene copolymer having secondary amine terminal groups as a toughener |
| US7649060B2 (en) | 2005-12-02 | 2010-01-19 | Henkel Corporation | Curable compositions |
| US7666938B2 (en) | 2004-12-03 | 2010-02-23 | Henkel Corporation | Nanoparticle silica filled benzoxazine compositions |
| US7709579B2 (en) | 2003-08-18 | 2010-05-04 | Henkel Corporation | Curable compositions for advanced processes, and products made therefrom |
| US8029889B1 (en) | 2004-12-03 | 2011-10-04 | Henkel Corporation | Prepregs, towpregs and preforms |
| CN113547656A (en) * | 2021-07-22 | 2021-10-26 | 安徽昊华环保科技有限公司 | Production method of corrosion-resistant rubber molded sieve plate |
-
1999
- 1999-03-23 JP JP11078683A patent/JP2000273291A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005000955A1 (en) * | 2003-06-27 | 2005-01-06 | Henkel Corporation | Heat curable compositions comprising a benzoxazine component and an acrylonitrile-butadiene copolymer having secondary amine terminal groups as a toughener |
| US7157509B2 (en) | 2003-06-27 | 2007-01-02 | Henkel Corporation | Curable compositions |
| US7649037B1 (en) | 2003-06-27 | 2010-01-19 | Henkel Corporation | Curable compositions |
| KR101138121B1 (en) * | 2003-06-27 | 2012-04-23 | 헨켈 코포레이션 | Heat curable compositions comprising a benzoxazine component and an acrylonitrile-butadiene copolymer having secondary amine terminal groups as a toughener |
| US7709579B2 (en) | 2003-08-18 | 2010-05-04 | Henkel Corporation | Curable compositions for advanced processes, and products made therefrom |
| US7666938B2 (en) | 2004-12-03 | 2010-02-23 | Henkel Corporation | Nanoparticle silica filled benzoxazine compositions |
| US8029889B1 (en) | 2004-12-03 | 2011-10-04 | Henkel Corporation | Prepregs, towpregs and preforms |
| US7649060B2 (en) | 2005-12-02 | 2010-01-19 | Henkel Corporation | Curable compositions |
| CN113547656A (en) * | 2021-07-22 | 2021-10-26 | 安徽昊华环保科技有限公司 | Production method of corrosion-resistant rubber molded sieve plate |
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