JPH10292031A - Epoxy resin composition, prepreg and laminate - Google Patents

Epoxy resin composition, prepreg and laminate

Info

Publication number
JPH10292031A
JPH10292031A JP7813197A JP7813197A JPH10292031A JP H10292031 A JPH10292031 A JP H10292031A JP 7813197 A JP7813197 A JP 7813197A JP 7813197 A JP7813197 A JP 7813197A JP H10292031 A JPH10292031 A JP H10292031A
Authority
JP
Japan
Prior art keywords
epoxy resin
resin composition
epoxy
molecular weight
laminate
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.)
Granted
Application number
JP7813197A
Other languages
Japanese (ja)
Other versions
JP3570147B2 (en
Inventor
Hiroshi Yamamoto
広志 山本
Kamio Yonemoto
神夫 米本
Yoshihide Sawa
佳秀 澤
Eiichiro Saito
英一郎 斉藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Original Assignee
Matsushita Electric Works Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Works Ltd filed Critical Matsushita Electric Works Ltd
Priority to JP07813197A priority Critical patent/JP3570147B2/en
Publication of JPH10292031A publication Critical patent/JPH10292031A/en
Application granted granted Critical
Publication of JP3570147B2 publication Critical patent/JP3570147B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Landscapes

  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a composition excellent in bonding strength by mixing a modified phenol product obtained by reacting a polyphenylene resin with a phenolic compound having at least the specified number of hydorxyl groups in the presence of a reaction initiator and having a number-average molecular weight corresponding to a specified percentage of that of the starting resin with an epoxy resin having at least the specified number of epoxy groups in the molecule and a curing agent. SOLUTION: A polyphenylene resin is subjected to a redistribution reaction with a phenolic compound to form a modified phenol product having a number- average molecular weight corresponding to 5-70% of that (10,000-30,000) of the starting resin. It is desirably 1,000-3,000. It is desirable that the phenolic compound is one having at least two phenolic hydroxyl groups in the molecule and that an epoxy resin having at least three epoxy groups in the molecule, especially a resin of formula I or II is contained in an amount of 1-40 pts.wt. per 100 pts.wt. total epoxy resin. It is desirable that the reaction initiator is benzoyl peroxide. A laminate excellent in strength of bonding between the surface metal foil and a bonding wire can be obtained.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、たとえば高周波領
域で使用されるプリント配線板に用いられる積層板、こ
の積層板の製造に用いられるプリプレグ、及びこのプリ
プレグの製造に用いられるエポキシ樹脂組成物に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate used for a printed wiring board used in, for example, a high frequency region, a prepreg used for producing the laminate, and an epoxy resin composition used for producing the prepreg. Things.

【０００２】[0002]

【従来の技術】衛星通信などに用いられるＸバンド（８
〜１２ＧＨｚ）領域、いわゆる超高周波領域で使用する
プリント配線板の製造に用いられる積層板には、広い高
周波範囲、温度範囲及び湿度範囲で誘電率及び誘電正接
がいずれも一定で、かつ、好ましくは誘電正接が小さい
ことが望まれており、このような用途にエポキシ樹脂及
びポリフェニレンエーテル樹脂（以下、ＰＰＥと記す）
を含有するエポキシ樹脂組成物を用いた積層板が使用さ
れている。2. Description of the Related Art An X band (8
(12 GHz) region, that is, a laminated board used for manufacturing a printed wiring board used in a so-called ultra-high frequency region, the dielectric constant and the dielectric loss tangent are both constant over a wide high frequency range, temperature range and humidity range, and preferably, It is desired that the dielectric loss tangent is small. For such applications, epoxy resin and polyphenylene ether resin (hereinafter referred to as PPE) are used.
Laminated boards using an epoxy resin composition containing

【０００３】従来、このエポキシ樹脂及びＰＰＥを含有
するエポキシ樹脂組成物を用いた積層板としては、エポ
キシ樹脂とＰＰＥを単に配合したエポキシ樹脂組成物を
用いた、エポキシ樹脂とＰＰＥの硬化物が化学的に独立
して存在する積層板や、エポキシ樹脂のエポキシ基とＰ
ＰＥの末端水酸基とを反応させることにより、ＰＰＥと
エポキシ樹脂が架橋した硬化物よりなる積層板が検討さ
れている。Conventionally, as a laminate using the epoxy resin composition containing the epoxy resin and the PPE, a cured product of the epoxy resin and the PPE using an epoxy resin composition obtained by simply blending the epoxy resin and the PPE is used. Laminates that exist independently of each other, or the epoxy group of epoxy resin and P
A laminate made of a cured product in which PPE and an epoxy resin are crosslinked by reacting with a terminal hydroxyl group of PE has been studied.

【０００４】これらのうち前者の積層板は、アルカリや
クロロホルムに浸漬して耐アルカリ性試験や耐溶剤性試
験を行うと、エポキシ樹脂とＰＰＥの結合が不十分なた
めに層間剥離が発生する場合があるという問題があり、
また、後者の積層板は、用いたＰＰＥが高分子量の場
合、ＰＰＥの末端フェノール性水酸基とエポキシ樹脂の
エポキシ基との反応性が低く、硬化物中に架橋構造に関
与しない未反応のＰＰＥが多量存在するため、層間接着
強度が低いという問題や、前者の積層板と同様に耐溶剤
性試験を行うと、前者の積層板と比較すると優れるが、
依然として層間剥離が発生する場合があるという問題が
あった。When the former laminate is immersed in alkali or chloroform and subjected to an alkali resistance test or a solvent resistance test, delamination may occur due to insufficient bonding between the epoxy resin and PPE. There is a problem that there is
In the latter laminate, when the used PPE has a high molecular weight, the reactivity between the terminal phenolic hydroxyl group of the PPE and the epoxy group of the epoxy resin is low, and unreacted PPE which does not participate in the crosslinked structure is contained in the cured product. Due to the presence of a large amount, the problem of low interlayer adhesion strength, and when the solvent resistance test is performed in the same manner as the former laminate, it is superior to the former laminate,
There has been a problem that delamination may still occur.

【０００５】そのため、高分子量のＰＰＥとフェノール
性化合物を、過酸化物等の反応開始剤存在下で反応させ
ることにより、用いたＰＰＥの数平均分子量より低分子
量の、ＰＰＥで変成した変成フェノール生成物を製造
し、その変成フェノール生成物とエポキシ樹脂を配合し
たエポキシ樹脂組成物を用いて、耐溶剤性が優れた積層
板を製造することが検討されている。この積層板の場
合、変成フェノール生成物のフェノール性水酸基とエポ
キシ樹脂のエポキシ基との反応により、ＰＰＥが硬化物
中の架橋構造に取り込まれるため、耐溶剤性が優れると
考えられている。[0005] Therefore, by reacting a high molecular weight PPE with a phenolic compound in the presence of a reaction initiator such as a peroxide, a modified phenol modified by PPE having a molecular weight lower than the number average molecular weight of the used PPE is produced. It has been studied to produce a laminate having excellent solvent resistance using an epoxy resin composition obtained by mixing a modified phenol product and an epoxy resin. In the case of this laminate, it is considered that PPE is taken into the crosslinked structure in the cured product by the reaction between the phenolic hydroxyl group of the modified phenol product and the epoxy group of the epoxy resin, so that the solvent resistance is excellent.

【０００６】しかし、この変成フェノール生成物とエポ
キシ樹脂を含有するエポキシ樹脂組成物を用いて表面に
銅箔等の層を有する積層板を製造した後、半導体チップ
と接続するために、金線等のボンディングワイヤーを積
層板表面の金属箔と接合した場合、加熱時のボンディン
グワイヤーと金属箔の接着強度の評価において、ボンデ
ィングワイヤーと金属箔の接合部が剥がれる場合があ
り、改良の余地があった。However, after manufacturing a laminate having a layer such as a copper foil on the surface using the epoxy resin composition containing the modified phenol product and the epoxy resin, a gold wire or the like is used for connection with a semiconductor chip. When bonding the bonding wire with the metal foil on the surface of the laminated board, in the evaluation of the bonding strength between the bonding wire and the metal foil at the time of heating, the bonding portion between the bonding wire and the metal foil may be peeled off, and there is room for improvement. .

【０００７】そのため、高周波領域で使用する積層板に
要求される特性である、誘電率、誘電正接及びはんだ耐
熱性を低下することなしに、その表面に有する金属箔に
ボンディングワイヤーを接合した場合に、その接合部の
接着強度が優れる積層板が求められている。Therefore, when a bonding wire is bonded to a metal foil on its surface without deteriorating the dielectric constant, dielectric loss tangent, and solder heat resistance, which are characteristics required for a laminate used in a high-frequency region. There is a demand for a laminate having excellent bonding strength at the joint.

【０００８】[0008]

【発明が解決しようとする課題】本発明は、上記問題点
を改善するために成されたもので、その目的とするとこ
ろは、ＰＰＥとフェノール性化合物を反応開始剤の存在
下で反応させてなる変成フェノール生成物及びエポキシ
樹脂を含有するエポキシ樹脂組成物であって、誘電率、
誘電正接及びはんだ耐熱性を低下することなしに、その
表面に有する金属箔にボンディングワイヤーを接合した
場合に、金属箔とボンディングワイヤーとの接着強度が
優れた金属箔張りの積層板が得られるエポキシ樹脂組成
物を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to react PPE with a phenolic compound in the presence of a reaction initiator. An epoxy resin composition comprising a modified phenol product and an epoxy resin, comprising:
When bonding wires are bonded to the metal foil on the surface without lowering the dielectric loss tangent and solder heat resistance, an epoxy with a metal foil-clad laminate with excellent adhesive strength between the metal foil and the bonding wires is obtained. It is to provide a resin composition.

【０００９】また、誘電率、誘電正接及びはんだ耐熱性
を低下することなしに、その表面に有する金属箔にボン
ディングワイヤーを接合した場合に、金属箔とボンディ
ングワイヤーとの接着強度が優れた金属箔張りの積層板
が得られるプリプレグを提供することにある。Further, when a bonding wire is bonded to a metal foil on the surface thereof without lowering the dielectric constant, the dielectric loss tangent, and the heat resistance of the solder, the metal foil has excellent adhesion strength between the metal foil and the bonding wire. An object of the present invention is to provide a prepreg from which a laminated board can be obtained.

【００１０】また、誘電率、誘電正接及びはんだ耐熱性
が優れると共に、その表面に有する金属箔にボンディン
グワイヤーを接合した場合に、金属箔とボンディングワ
イヤーとの接着強度が優れた積層板を提供することにあ
る。Further, the present invention provides a laminate having excellent dielectric constant, dielectric loss tangent, and soldering heat resistance, and having excellent bonding strength between the metal foil and the bonding wire when the bonding wire is bonded to the metal foil on the surface thereof. It is in.

【００１１】[0011]

【課題を解決するための手段】本発明の請求項１に係る
エポキシ樹脂組成物は、数平均分子量が１００００〜３
００００のＰＰＥとフェノール性化合物を反応開始剤の
存在下で再分配反応させて、数平均分子量が用いたＰＰ
Ｅの数平均分子量の５〜７０％になるように反応させた
変成フェノール生成物、エポキシ樹脂及びエポキシ樹脂
の硬化剤とを含有するエポキシ樹脂組成物において、エ
ポキシ樹脂として、分子内にエポキシ基を３個以上有す
るエポキシ樹脂を含有することを特徴とする。The epoxy resin composition according to claim 1 of the present invention has a number average molecular weight of 10,000 to 3.
0000 PPE and a phenolic compound are redistributed in the presence of a reaction initiator to obtain a PP having a number average molecular weight.
In an epoxy resin composition containing a modified phenol product reacted so as to have a number average molecular weight of 5 to 70% of E, an epoxy resin, and a curing agent for the epoxy resin, an epoxy group in the molecule is used as the epoxy resin. It is characterized by containing three or more epoxy resins.

【００１２】本発明の請求項２に係るエポキシ樹脂組成
物は、請求項１記載のエポキシ樹脂組成物において、分
子内にエポキシ基を３個以上有するエポキシ樹脂を、全
エポキシ樹脂１００重量部中に１〜４０重量部含有する
ことを特徴とする。According to a second aspect of the present invention, there is provided the epoxy resin composition according to the first aspect, wherein the epoxy resin having three or more epoxy groups in a molecule is contained in 100 parts by weight of the total epoxy resin. It is characterized by containing 1 to 40 parts by weight.

【００１３】本発明の請求項３に係るエポキシ樹脂組成
物は、請求項１又は請求項２記載のエポキシ樹脂組成物
において、分子内にエポキシ基を３個以上有するエポキ
シ樹脂として、下記式（ａ）で表されるエポキシ樹脂を
含有することを特徴とする。The epoxy resin composition according to a third aspect of the present invention is the epoxy resin composition according to the first or second aspect, wherein the epoxy resin having three or more epoxy groups in the molecule has the following formula (a) ) Is contained.

【００１４】[0014]

【化３】 Embedded image

【００１５】本発明の請求項４に係るエポキシ樹脂組成
物は、請求項１又は請求項２記載のエポキシ樹脂組成物
において、分子内にエポキシ基を３個以上有するエポキ
シ樹脂として、下記式（ｂ）で表されるエポキシ樹脂を
含有することを特徴とする。The epoxy resin composition according to a fourth aspect of the present invention is the epoxy resin composition according to the first or second aspect, wherein the epoxy resin having three or more epoxy groups in the molecule is represented by the following formula (b): ) Is contained.

【００１６】[0016]

【化４】 Embedded image

【００１７】本発明の請求項５に係るエポキシ樹脂組成
物は、請求項１から請求項４のいずれかに記載のエポキ
シ樹脂組成物において、変成フェノール生成物の数平均
分子量が、１０００〜３０００であることを特徴とす
る。The epoxy resin composition according to claim 5 of the present invention is the epoxy resin composition according to any one of claims 1 to 4, wherein the modified phenol product has a number average molecular weight of 1,000 to 3,000. It is characterized by.

【００１８】本発明の請求項６に係るエポキシ樹脂組成
物は、請求項１から請求項５のいずれかに記載のエポキ
シ樹脂組成物において、反応開始剤が、過酸化ベンゾイ
ルであることを特徴とする。The epoxy resin composition according to claim 6 of the present invention is characterized in that, in the epoxy resin composition according to any one of claims 1 to 5, the reaction initiator is benzoyl peroxide. I do.

【００１９】本発明の請求項７に係るエポキシ樹脂組成
物は、請求項１から請求項６のいずれかに記載のエポキ
シ樹脂組成物において、フェノール性化合物が、分子内
に２個以上のフェノール性水酸基を有するフェノール性
化合物であることを特徴とする。The epoxy resin composition according to claim 7 of the present invention is the epoxy resin composition according to any one of claims 1 to 6, wherein the phenolic compound has two or more phenolic compounds in the molecule. It is a phenolic compound having a hydroxyl group.

【００２０】本発明の請求項８に係るプリプレグは、請
求項１から請求項７のいずれかに記載のエポキシ樹脂組
成物を、基材に含浸乾燥してなる。A prepreg according to claim 8 of the present invention is obtained by impregnating and drying a substrate with the epoxy resin composition according to any one of claims 1 to 7.

【００２１】本発明の請求項９に係る積層板は、請求項
８記載のプリプレグに金属箔を重ねて加熱・加圧してな
る。According to a ninth aspect of the present invention, there is provided a laminated plate comprising a prepreg according to the eighth aspect, a metal foil superposed thereon, and heating and pressing.

【００２２】本発明によると、エポキシ樹脂組成物に、
分子内にエポキシ基を３個以上有するエポキシ樹脂を含
有するため、その表面に有する金属箔とボンディングワ
イヤーとの接着強度が優れた積層板が得られる。また、
分子内にエポキシ基を３個以上有するエポキシ樹脂は、
上記変成フェノール生成物と架橋して両者が架橋構造に
取り込まれるため、エポキシ樹脂とＰＰＥとの特性が損
なわれず、誘電率、誘電正接及びはんだ耐熱性等も優れ
た積層板が得られる。According to the present invention, the epoxy resin composition comprises:
Since it contains an epoxy resin having three or more epoxy groups in the molecule, a laminate having excellent adhesion strength between the metal foil and the bonding wire on the surface thereof can be obtained. Also,
Epoxy resin having three or more epoxy groups in the molecule,
Since the modified phenol product is cross-linked and incorporated into the cross-linked structure, the properties of the epoxy resin and PPE are not impaired, and a laminate having excellent dielectric constant, dielectric loss tangent, solder heat resistance, and the like can be obtained.

【００２３】[0023]

【発明の実施の形態】本発明の請求項１から請求項７に
係るエポキシ樹脂組成物は、数平均分子量が１００００
〜３００００のＰＰＥとフェノール性化合物を反応開始
剤の存在下で再分配反応させて、その数平均分子量が用
いたＰＰＥの数平均分子量の５〜７０％の数平均分子量
になるように反応させてなる変成フェノール生成物、エ
ポキシ樹脂及びエポキシ樹脂の硬化剤を、少なくとも含
有する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin composition according to any one of claims 1 to 7 of the present invention has a number average molecular weight of 10,000.
A redistribution reaction is carried out between の 30,000 PPE and a phenolic compound in the presence of a reaction initiator so that the number average molecular weight of the phenolic compound becomes 5 to 70% of the number average molecular weight of the used PPE. At least a modified phenol product, an epoxy resin and a curing agent for the epoxy resin.

【００２４】変成フェノール生成物の製造に用いられる
ＰＰＥは、別名ポリフェニレンオキサイド樹脂とも呼ば
れる樹脂であり、その一例としては、ポリ（２，６−ジ
メチル−１，４−フェニレンオキサイド）が挙げられ
る。このようなＰＰＥは、例えば、ＵＳＰ４０５９５６
８号明細書に開示されている方法で合成することができ
る。The PPE used for the production of the modified phenol product is a resin also called a polyphenylene oxide resin. One example is poly (2,6-dimethyl-1,4-phenylene oxide). Such PPE is described, for example, in US Pat.
No. 8 can be synthesized by the method disclosed in the specification.

【００２５】変成フェノール生成物の製造に用いられる
フェノール性化合物としては、例えば、ビスフェノール
Ａ、ビスフェノールＦ、フェノ−ルノボラック、クレゾ
ールノボラック等が挙げられる。なお、フェノール性水
酸基を分子内に２個以上有するフェノール類を用いると
好ましい。このフェノール類のフェノール性水酸基数の
上限は特に限定するものではないが、分子内に３０個以
下のものが一般に用いられる。なお、フェノール性化合
物の量は、ＰＰＥ１００重量部に対して１〜２０重量部
が適量であり、反応開始剤と同程度の量が一般的であ
る。Examples of the phenolic compound used for producing the modified phenol product include bisphenol A, bisphenol F, phenol novolak, cresol novolak and the like. Note that it is preferable to use a phenol having two or more phenolic hydroxyl groups in the molecule. The upper limit of the number of phenolic hydroxyl groups of the phenols is not particularly limited, but those having 30 or less in the molecule are generally used. The appropriate amount of the phenolic compound is 1 to 20 parts by weight based on 100 parts by weight of PPE, and is generally the same as the amount of the reaction initiator.

【００２６】変成フェノール生成物の製造に用いられる
反応開始剤としては、過酸化ベンゾイル、ジクミルパー
オキサイド、ｔ−ブチルクミルパーオキサイド、ジ−ｔ
−ブチルパーオキサイド、２，５−ジメチル−２，５−
ジ−ｔ−ブチルパーオキシへキシン−３、２，５−ジメ
チル−２，５−ジ−ｔ−ブチルパーオキシヘキサン、
α，α’−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロ
ピル）ベンゼンなどの過酸化物があげられる。また過酸
化物ではないが、市販の反応開始剤である日本油脂株式
会社製の商品名「ビスクミル」（１分半減温度３３０
℃）を使用することもできる。なお、過酸化ベンゾイル
を用いると、反応性が優れ好ましい。なお、反応開始剤
の量は、ＰＰＥ１００重量部に対して１〜２０重量部が
適量である。The reaction initiator used for producing the modified phenol product includes benzoyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t
-Butyl peroxide, 2,5-dimethyl-2,5-
Di-tert-butylperoxyhexine-3, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane,
peroxides such as α, α′-bis (t-butylperoxy-m-isopropyl) benzene. Although it is not a peroxide, it is a commercially available reaction initiator “Biscumil” manufactured by NOF Corporation (1 minute half-life temperature 330
° C) can also be used. The use of benzoyl peroxide is preferred because of its excellent reactivity. The appropriate amount of the reaction initiator is 1 to 20 parts by weight based on 100 parts by weight of PPE.

【００２７】そして変成フェノール生成物を製造する場
合には、有機溶媒中で、上記のＰＰＥとフェノール性化
合物を反応開始剤の存在下で再分配反応させて、用いた
ＰＰＥの数平均分子量より低分子量の変成フェノール生
成物を製造する。再分配反応の条件としては、例えば、
上記のＰＰＥとフェノール性化合物と反応開始剤を撹拌
しながら、８０〜１２０℃で１０〜１００分程度加熱し
て行う。なお、用いる有機溶媒としては、トルエン、ベ
ンゼン、キシレン等の芳香族炭化水素系溶媒が挙げられ
る。In the case of producing a modified phenol product, the above-mentioned PPE and the phenolic compound are redistributed in an organic solvent in the presence of a reaction initiator, so that the PPE is lower than the number average molecular weight of the used PPE. Produce a modified phenolic product of molecular weight. Conditions for the redistribution reaction include, for example,
The above-mentioned PPE, the phenolic compound and the reaction initiator are stirred and heated at 80 to 120 ° C. for about 10 to 100 minutes. In addition, as an organic solvent to be used, aromatic hydrocarbon solvents such as toluene, benzene, and xylene are exemplified.

【００２８】反応開始剤の存在下で数平均分子量が１０
０００〜３００００のＰＰＥとフェノール性化合物を反
応させると、先ずＰＰＥがラジカル化されると考えら
れ、直鎖が切断される再分配反応が進行してＰＰＥが低
分子量化し、この低分子量化したＰＰＥでフェノール性
化合物が変成される。In the presence of a reaction initiator, the number average molecular weight is 10
When a phenolic compound is reacted with PPE having a molecular weight of 3,000 to 30,000, it is considered that the PPE is radicalized first, and a redistribution reaction in which straight chains are cut proceeds to reduce the molecular weight of the PPE. The phenolic compound is modified.

【００２９】そして得られる変成フェノール生成物の構
造は、低分子化したＰＰＥの一方又は両方の末端部にフ
ェノール性化合物が結合して、ＰＰＥの一方又は両末端
にフェノール性水酸基を有する構造となると考えられ
る。そのため、この末端のフェノール性水酸基がエポキ
シ樹脂のエポキシ基と反応し、ＰＰＥとエポキシ樹脂が
強固に架橋すると考えられる。The resulting modified phenol product has a structure in which a phenolic compound is bonded to one or both terminals of a low-molecular-weight PPE to have a structure having a phenolic hydroxyl group at one or both terminals of the PPE. Conceivable. Therefore, it is considered that this terminal phenolic hydroxyl group reacts with the epoxy group of the epoxy resin, and the PPE and the epoxy resin are strongly crosslinked.

【００３０】なお、再分配反応して得られる変成フェノ
ール生成物の数平均分子量は、用いたＰＰＥの数平均分
子量の５〜７０％の数平均分子量であることが重要であ
る。７０％を越える場合、エポキシ樹脂組成物の粘度が
高くなって、基材に含浸するときの含浸性が低下し、得
られるプリプレグの樹脂付着量がばらついたり、プリプ
レグの取り扱い時に樹脂が剥がれて樹脂付着量がばらつ
き、電気特性のばらつきが発生する場合がある。また、
５％未満の場合、得られる積層板の機械的強度や耐熱性
が低下する場合がある。It is important that the modified phenol product obtained by the redistribution reaction has a number average molecular weight of 5 to 70% of the number average molecular weight of the PPE used. If it exceeds 70%, the viscosity of the epoxy resin composition increases, the impregnation property when impregnating the base material decreases, the amount of resin adhered to the obtained prepreg varies, and the resin is peeled off when the prepreg is handled. In some cases, the amount of adhesion varies and the electrical characteristics vary. Also,
If it is less than 5%, the mechanical strength and heat resistance of the obtained laminate may decrease.

【００３１】なお、数平均分子量が１０００〜３０００
の場合、得られるエポキシ樹脂組成物を基材に含浸する
ときの含浸性が特に優れ好ましい。なお、変成フェノー
ル生成物の数平均分子量が、用いたＰＰＥの数平均分子
量の７０％を越える場合、エポキシ樹脂組成物の保存性
が低下して粘度が短期間で高くなりやすく、エポキシ樹
脂組成物の使用可能な時間が短くなって、生産に支障を
来しやすいという問題も発生しやすくなる。The number average molecular weight is 1,000 to 3,000.
In the case of the above, the impregnating property when impregnating the substrate with the obtained epoxy resin composition is particularly excellent and preferable. When the number average molecular weight of the modified phenol product exceeds 70% of the number average molecular weight of the PPE used, the storage stability of the epoxy resin composition is reduced and the viscosity tends to increase in a short period of time. The possible time is shortened, and the problem that production is likely to be hindered is likely to occur.

【００３２】なお、用いたＰＰＥが複数の数平均分子量
のＰＰＥの混合物の場合には、その混合物の平均値に対
して、５〜７０％の数平均分子量となるように反応させ
る。また、得ようとする変成フェノール生成物の数平均
分子量の調整は、反応開始剤の量を増やすと数平均分子
量が低下する傾向があるため、反応開始剤の量で調整す
ると調整しやすく好ましい。When the PPE used is a mixture of a plurality of PPEs having a number average molecular weight, the reaction is carried out so that the number average molecular weight is 5 to 70% with respect to the average value of the mixture. The number average molecular weight of the modified phenol product to be obtained is preferably adjusted by adjusting the amount of the reaction initiator since the number average molecular weight tends to decrease when the amount of the reaction initiator is increased.

【００３３】エポキシ樹脂組成物に含有するエポキシ樹
脂には、分子内にエポキシ基を３個以上有するエポキシ
樹脂（以下、多官能樹脂と記す）を含有することが重要
である。多官能樹脂を含有しない場合は、このエポキシ
樹脂組成物を用いて表面に金属箔の層を有する積層板を
製造し、ボンディングワイヤーを積層板表面の金属箔と
接合した後、ボンディングワイヤーと金属箔との接着強
度の評価を行うと、ボンディングワイヤーと金属箔の接
合部で剥がれる場合がある。It is important that the epoxy resin contained in the epoxy resin composition contains an epoxy resin having three or more epoxy groups in a molecule (hereinafter, referred to as a polyfunctional resin). When the polyfunctional resin is not contained, a laminate having a metal foil layer on the surface is manufactured using the epoxy resin composition, and the bonding wire is joined to the metal foil on the laminate surface. When the evaluation of the adhesive strength with the bonding wire is performed, the bonding wire and the metal foil may be peeled off at the joint.

【００３４】この多官能樹脂としては、上記式（ａ）で
表されるエポキシ樹脂や、上記式（ｂ）で表されるエポ
キシ樹脂や、下記式（ｃ）で表される一般にノボラック
型エポキシ樹脂と呼ばれるエポキシ樹脂等が挙げられ
る。なお、上記式（ａ）で表されるエポキシ樹脂、又
は、上記式（ｂ）で表されるエポキシ樹脂を用いると、
金属箔とボンディングワイヤーとの接着強度が特に優れ
た積層板が得られ好ましい。Examples of the polyfunctional resin include an epoxy resin represented by the above formula (a), an epoxy resin represented by the above formula (b), and a generally novolac epoxy resin represented by the following formula (c). And the like. When the epoxy resin represented by the formula (a) or the epoxy resin represented by the formula (b) is used,
It is preferable because a laminate having particularly excellent adhesion strength between the metal foil and the bonding wire is obtained.

【００３５】[0035]

【化５】 Embedded image

【００３６】なお、多官能樹脂の分子内のエポキシ基の
数は、３個以上であれは特に限定するものではないが、
あまり多いとエポキシ樹脂組成物の粘度が高くなって、
基材への含浸性が低下するため、３〜３０個の範囲のも
のを使用すると好ましい。なお、上記式（ａ）で表され
るエポキシ樹脂や、上記式（ｃ）で表されるエポキシ樹
脂を用いる場合、多官能樹脂１００重量部中に、エポキ
シ基を３個有するエポキシ樹脂を５０重量部程度含有す
ると、基材への含浸性、及び金属箔とボンディングワイ
ヤーとの接着強度を向上させる効果のバランスがよく好
ましい。The number of epoxy groups in the molecule of the polyfunctional resin is not particularly limited as long as it is three or more.
If too much, the viscosity of the epoxy resin composition increases,
Since the impregnating property to the base material is reduced, it is preferable to use one in the range of 3 to 30. When the epoxy resin represented by the above formula (a) or the epoxy resin represented by the above formula (c) is used, 50 parts by weight of the epoxy resin having three epoxy groups per 100 parts by weight of the polyfunctional resin. When it is contained in an amount of about part, the balance between the impregnating property of the base material and the effect of improving the adhesive strength between the metal foil and the bonding wire is preferable.

【００３７】なお、エポキシ樹脂組成物に含有するエポ
キシ樹脂は、多官能樹脂のみに限定するものではなく、
分子内にエポキシ基を２個有するエポキシ樹脂をも含有
することにより、多官能樹脂を、全エポキシ樹脂１００
重量部中に１〜４０重量部含有するようにすると、金属
箔とボンディングワイヤーとの接着強度が優れると共
に、耐熱性が優れた積層板が得られ好ましい。１重量部
未満の場合は、金属箔とボンディングワイヤーとの接着
強度を向上させる効果が小さく、４０重量部を越えると
吸湿率が高くなってはんだ耐熱性が低下する場合があ
る。The epoxy resin contained in the epoxy resin composition is not limited to only a polyfunctional resin.
By containing an epoxy resin having two epoxy groups in the molecule, the polyfunctional resin can be converted into a total epoxy resin 100%.
When the content is 1 to 40 parts by weight per part by weight, a laminate having excellent adhesive strength between the metal foil and the bonding wire and excellent heat resistance can be obtained. When the amount is less than 1 part by weight, the effect of improving the bonding strength between the metal foil and the bonding wire is small. When the amount exceeds 40 parts by weight, the moisture absorption rate is increased and the solder heat resistance may be reduced.

【００３８】分子内にエポキシ基を２個有するエポキシ
樹脂としては、例えば、ビスフェノ−ルＡ型エポキシ樹
脂、ビスフェノ−ルＦ型エポキシ樹脂、ビスフェノ−ル
Ｓ型エポキシ樹脂、ヒダントイン型エポキシ樹脂、脂環
式エポキシ樹脂、ビフェニル型エポキシ樹脂、及びこれ
らの樹脂をハロゲン化したエポキシ樹脂等が挙げられ、
２種類以上を併用してもよい。なお、分子内にエポキシ
基を１個有するエポキシ樹脂をも併用することもでき
る。Examples of the epoxy resin having two epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydantoin type epoxy resin, and alicyclic ring. Formula epoxy resins, biphenyl type epoxy resins, and epoxy resins obtained by halogenating these resins.
Two or more types may be used in combination. In addition, an epoxy resin having one epoxy group in the molecule may be used in combination.

【００３９】エポキシ樹脂組成物に含有するエポキシ樹
脂の硬化剤としては、例えばジシアンジアミド、脂肪族
ポリアミド等のアミド系硬化剤や、ジアミノジフェニル
メタン、メタフェニレンジアミン、アンモニア、トリエ
チルアミン、ジエチルアミン等のアミン系硬化剤や、ビ
スフェノールＡ、ビスフェノールＦ、フェノールノボラ
ック樹脂、クレゾールノボラック樹脂、ｐ−キシレン−
ノボラック樹脂等のフェノール系硬化剤や、酸無水物類
等が挙げられ、２種類以上を併用してもよい。Examples of the curing agent for the epoxy resin contained in the epoxy resin composition include amide curing agents such as dicyandiamide and aliphatic polyamide, and amine curing agents such as diaminodiphenylmethane, metaphenylenediamine, ammonia, triethylamine and diethylamine. Or bisphenol A, bisphenol F, phenol novolak resin, cresol novolak resin, p-xylene-
Examples include phenolic curing agents such as novolak resins, acid anhydrides, and the like, and two or more kinds may be used in combination.

【００４０】なお、エポキシ樹脂組成物には硬化反応を
促進するために、硬化促進剤の添加が現実的である。含
有することができる硬化促進剤としては、例えば、２−
メチルイミダゾール、２−エチル−４−メチルイミダゾ
ール、２−フェニルイミダゾール等のイミダゾール類、
１，８−ジアザ−ビシクロ［５．４．０］ウンデセン−
７、トリエチレンジアミン、ベンジルジメチルアミン等
の三級アミン類、トリブチルホスフィン、トリフェニル
ホスフィン等の有機ホスフィン類、テトラフェニルホス
ホニウムテトラフェニルボレート、トリフェニルホスフ
ィンテトラフェニルボレート等のテトラフェニルボロン
塩等が挙げられ、２種類以上を併用してもよい。Incidentally, it is practical to add a curing accelerator to the epoxy resin composition in order to accelerate the curing reaction. As the curing accelerator that can be contained, for example, 2-
Imidazoles such as methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,
1,8-diaza-bicyclo [5.4.0] undecene-
7, tertiary amines such as triethylenediamine and benzyldimethylamine; organic phosphines such as tributylphosphine and triphenylphosphine; and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate. Two or more types may be used in combination.

【００４１】なお、エポキシ樹脂組成物には、必要に応
じて無機充填材や、溶剤等を含有することができる。含
有することができる無機充填材としては、二酸化チタン
系セラミック、チタン酸バリウム系セラミック、チタン
酸鉛系セラミック、チタン酸ストロンチウム系セラミッ
ク、チタン酸カルシウム系セラミック、チタン酸ビスマ
ス系セラミック、チタン酸マグネシウム系セラミック、
ジルコン酸鉛系セラミック等の、誘電率が１００以上の
無機充填材や、シリカ粉体、ガラス繊維、タルク等が挙
げられ、２種類以上を併用してもよい。誘電率が１００
以上の無機充填材を含有すると、高周波特性が特に優れ
好ましい。また、含有することができる溶剤としては、
トルエン、キシレン、ベンゼン、ケトン、アルコール類
等の有機系溶媒が挙げられる。The epoxy resin composition may contain an inorganic filler, a solvent, and the like, if necessary. As inorganic fillers that can be contained, titanium dioxide-based ceramics, barium titanate-based ceramics, lead titanate-based ceramics, strontium titanate-based ceramics, calcium titanate-based ceramics, bismuth titanate-based ceramics, magnesium titanate-based ceramics ceramic,
Examples include inorganic fillers having a dielectric constant of 100 or more, such as lead zirconate-based ceramics, silica powder, glass fibers, and talc. Two or more kinds may be used in combination. Dielectric constant is 100
When the inorganic filler described above is contained, the high-frequency characteristics are particularly excellent and are preferable. Further, as a solvent that can be contained,
Organic solvents such as toluene, xylene, benzene, ketone, and alcohols are exemplified.

【００４２】得られたエポキシ樹脂組成物を、基材に含
浸乾燥してプリプレグを製造する。エポキシ樹脂組成物
を、基材に含浸乾燥する方法としては特に限定するもの
ではなく、例えばエポキシ樹脂組成物中に基材を浸漬し
て含浸させた後、加熱して溶剤の除去や、エポキシ樹脂
組成物を半硬化させてプリプレグを製造する。基材に含
浸する樹脂量は特に限定しないが、乾燥後の樹脂含有量
が、プリプレグの重量に対して３０〜７０重量％となる
ように含浸すると、特に電気特性が優れた積層板が得ら
れ好ましい。The obtained epoxy resin composition is impregnated into a substrate and dried to produce a prepreg. The method of impregnating and drying the epoxy resin composition on the base material is not particularly limited. For example, after the base material is immersed and impregnated in the epoxy resin composition, the solvent is removed by heating and the epoxy resin is removed. The composition is semi-cured to produce a prepreg. The amount of resin impregnated in the base material is not particularly limited, but when the resin content after drying is impregnated so as to be 30 to 70% by weight with respect to the weight of the prepreg, a laminate having particularly excellent electric properties can be obtained. preferable.

【００４３】なお、含浸時にエポキシ樹脂組成物を２５
〜３５℃に保つと、基材への含浸性を安定させることが
でき、積層板の特性を良好にすることができる。また、
エポキシ樹脂組成物を含浸後、乾燥するに当たっては、
８０〜１８０℃の温度が好ましい。この乾燥が不十分で
あると、プリプレグ表面部分のみの乾燥に止まり、溶媒
が内部に残留する為にプリプレグの表面と内部との間で
樹脂の濃度差に起因する歪が生じ、プリプレグ表面に微
細なクラックが発生する場合がある。また、過度の乾燥
を行うと、プリプレグ表面では乾燥過程で急激な粘度変
化が起こるためにプリプレグ表面に筋むらや樹脂垂れが
発生し、金属箔とプリプレグとの密着性にばらつきが生
じ、その結果金属箔の引き剥がし強さや誘電特性等にば
らつきが発生する場合がある。In addition, at the time of impregnation, 25% of the epoxy resin composition was used.
When the temperature is maintained at ~ 35 ° C, the impregnation property of the substrate can be stabilized, and the characteristics of the laminate can be improved. Also,
After impregnating the epoxy resin composition, on drying,
Temperatures of 80-180 ° C are preferred. If this drying is insufficient, only the surface of the prepreg will be dried, and the solvent will remain inside, causing distortion due to the resin concentration difference between the surface and the inside of the prepreg. Cracks may occur. In addition, if excessive drying is performed, the viscosity of the prepreg surface changes drastically during the drying process, causing uneven streaks and resin dripping on the prepreg surface, resulting in variations in the adhesion between the metal foil and the prepreg. Variations may occur in the peel strength, dielectric properties, and the like of the metal foil.

【００４４】なお、エポキシ樹脂組成物を含浸する基材
としては、ガラスクロス、アラミドクロス、ポリエステ
ルクロス、ガラス不織布、アラミド不織布、ポリエステ
ル不織布、パルプ紙、リンター紙等が挙げられる。な
お、ガラスクロスを用いると、機械強度が優れた積層板
が得られ好ましい。なお、基材の厚みとしては０．０４
〜０．３ｍｍのものが一般的に使用される。The substrate impregnated with the epoxy resin composition includes glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, linter paper, and the like. In addition, it is preferable to use a glass cloth because a laminate having excellent mechanical strength can be obtained. The thickness of the substrate is 0.04
の も の 0.3 mm is commonly used.

【００４５】得られたプリプレグの所定枚数と金属箔を
重ねて被圧体とし、この被圧体を加熱・加圧して積層板
を製造する。金属箔としては、銅箔、アルミニウム箔等
が使用され、厚みとしては、０．０１２〜０．０７０ｍ
ｍのものが一般的に使用される。なお、銅箔を用いる
と、電気特性が優れた積層板が得られ好ましい。A predetermined number of the obtained prepregs and a metal foil are laminated to form a pressure-receiving body, and the pressure-receiving body is heated and pressed to produce a laminate. As the metal foil, copper foil, aluminum foil or the like is used, and as the thickness, 0.012 to 0.070 m
m are commonly used. In addition, it is preferable to use a copper foil because a laminate having excellent electric characteristics can be obtained.

【００４６】ＰＰＥで変成した変成フェノール生成物と
エポキシ樹脂とエポキシ樹脂の硬化剤の架橋反応は、主
としてエポキシ樹脂の硬化剤の反応温度に依存するた
め、エポキシ樹脂の硬化剤の種類に応じて加熱温度、加
熱時間を選ぶとよい。また加圧は、得られる積層板中に
気泡が残留しない程度の圧力に適宜調整して加圧する。
なお一般には、温度１５０〜３００℃、圧力１〜６ＭＰ
ａ、時間１０〜１２０分程度の条件で加熱・加圧する。The crosslinking reaction between the modified phenol product modified by PPE, the epoxy resin, and the curing agent for the epoxy resin mainly depends on the reaction temperature of the curing agent for the epoxy resin. It is good to choose temperature and heating time. The pressure is appropriately adjusted to such a level that no air bubbles remain in the obtained laminate, and the pressure is applied.
Generally, a temperature of 150 to 300 ° C. and a pressure of 1 to 6 MP
a, Heating and pressurizing under the conditions of about 10 to 120 minutes.

【００４７】このようにして得られた積層板は、エポキ
シ樹脂とＰＰＥの特性が損なわれないため、誘電特性等
の高周波特性や、はんだ耐熱性、接着強度等が優れると
共に、その表面に有する金属箔にボンディングワイヤー
を接合した場合に、金属箔とボンディングワイヤーとの
接着強度が優れた積層板となる。The laminate thus obtained does not impair the properties of the epoxy resin and the PPE, so that it has excellent high-frequency characteristics such as dielectric characteristics, solder heat resistance, adhesive strength, etc., and has a metal surface. When a bonding wire is bonded to the foil, a laminate having excellent adhesion strength between the metal foil and the bonding wire is obtained.

【００４８】なお、本発明のエポキシ樹脂組成物の使用
形態は、基材に含浸乾燥してプリプレグを製造する形態
に限るものではなく、たとえばキャスティング法により
基材を含まないシートを作成し、このシートをプリプレ
グに代用することもできる。このキャステング法による
方法は、例えばポリエステルフィルム、ポリイミドフィ
ルムなどの、エポキシ樹脂組成物が含有する溶媒に不溶
のシートに、エポキシ樹脂組成物を５〜７００μｍの厚
みに塗布し、乾燥した後シートを剥離して製造したり、
エポキシ樹脂組成物を熱溶融して押出成形により製造す
る。シートに塗布して製造する方法の場合、押出成形の
方法と比較すると比較的低温でより容易にシー卜を作る
ことができ好ましい。なお、エポキシ樹脂組成物を塗布
するシートは、離型剤で表面処理したシートを用いると
剥離が容易になるため生産性が優れ好ましい。The use form of the epoxy resin composition of the present invention is not limited to a form in which a base material is impregnated and dried to produce a prepreg. For example, a sheet containing no base material is prepared by a casting method. The sheet can be substituted for the prepreg. The method by the casting method is, for example, to apply the epoxy resin composition to a sheet insoluble in a solvent containing the epoxy resin composition, such as a polyester film and a polyimide film, to a thickness of 5 to 700 μm, and then, after drying, peel off the sheet. Manufacturing
The epoxy resin composition is hot-melted and manufactured by extrusion molding. In the case of the method of manufacturing by applying to a sheet, the sheet can be easily formed at a relatively low temperature as compared with the extrusion molding method, which is preferable. Note that the sheet to which the epoxy resin composition is applied is preferably excellent in productivity because the use of a sheet surface-treated with a release agent facilitates peeling.

【００４９】[0049]

【実施例】【Example】

（変成フェノール生成物の調整）数平均分子量２０００
０のＰＰＥ［日本Ｇ．Ｅ．プラスチック株式会社製、品
番６４０−１１１］、フェノール性化合物としてビスフ
ェノ−ルＡ、反応開始剤として過酸化ベンゾイル及び溶
剤としてトルエンを表１に示す割合（単位：重量部）で
配合し、９０℃で６０分間攪拌しながら再分配反応させ
て、液状の変成フェノール生成物（Ａ）〜（Ｇ）を得
た。この変成フェノール生成物（Ａ）〜（Ｇ）をゲル浸
透クロマトグラフ［カラム構成：東ソー株式会社製、Ｓ
ｕｐｅｒＨＭ−Ｍ（１本）＋ＳｕｐｅｒＨＭ−Ｈ（１
本）］にて分子量分布を測定し、数平均分子量を求め
た。その結果を表１に示す。なお、表１中、分子量比率
は、用いたＰＰＥの数平均分子量に対する、得られた変
成フェノール生成物の数平均分子量の比率を表す。(Preparation of modified phenol product) Number average molecular weight 2000
0 PPE [Japan G.P. E. FIG. Plastics Co., Ltd., product number 640-111], bisphenol A as a phenolic compound, benzoyl peroxide as a reaction initiator, and toluene as a solvent at a ratio shown in Table 1 (unit: parts by weight), and mixed at 90 ° C. A redistribution reaction was performed with stirring for 60 minutes to obtain liquid modified phenol products (A) to (G). The modified phenol products (A) to (G) were subjected to gel permeation chromatography [column configuration: manufactured by Tosoh Corporation, S
upperHM-M (1) + SuperHM-H (1
This) was used to measure the molecular weight distribution, and the number average molecular weight was determined. Table 1 shows the results. In Table 1, the molecular weight ratio represents the ratio of the number average molecular weight of the obtained modified phenol product to the number average molecular weight of the used PPE.

【００５０】[0050]

【表１】 [Table 1]

【００５１】（実施例１〜１３、比較例１〜５）変成フ
ェノール生成物（Ａ）〜（Ｇ）と、下記６種類のエポキ
シ樹脂と、エポキシ樹脂の硬化剤としてジアミノジフェ
ニルメタンと、硬化促進剤として２−エチル−４−メチ
ルイミダゾールと、溶剤としてトルエンとを表２及び表
３に示す割合（単位：重量部）でセパラブルフラスコに
入れ、室温で３０分間攪拌して空冷を行い２５℃のエポ
キシ樹脂組成物を得た。(Examples 1 to 13, Comparative Examples 1 to 5) Modified phenol products (A) to (G), the following six types of epoxy resins, diaminodiphenylmethane as a curing agent for the epoxy resin, and a curing accelerator , 2-ethyl-4-methylimidazole and toluene as a solvent were placed in a separable flask at the ratios shown in Tables 2 and 3 (unit: parts by weight), stirred at room temperature for 30 minutes, air-cooled, and cooled to 25 ° C. An epoxy resin composition was obtained.

【００５２】なお表２及び表３中、変成フェノール生成
物の配合重量は固形分としての重量を表す。また多官能
樹脂比率は、全エポキシ樹脂１００重量部中の多官能樹
脂の重量部を表す。In Tables 2 and 3, the compounding weight of the modified phenol product represents the weight as a solid content. In addition, the polyfunctional resin ratio indicates parts by weight of the polyfunctional resin in 100 parts by weight of the total epoxy resin.

【００５３】用いたエポキシ樹脂としては、 ・エポキシ樹脂ア：上記式（ａ）で表される多官能樹脂
［日本化薬株式会社製、商品名ＥＰＰＮ５０１Ｈ］（エ
ポキシ当量１６４）と、 ・エポキシ樹脂イ：上記式（ａ）で表される多官能樹脂
［油化シェルエポキシ株式会社製、商品名エピコート１
０３２］（エポキシ当量１７４）と、 ・エポキシ樹脂ウ：上記式（ａ）で表される多官能樹脂
［ダウケミカル株式会社製、商品名ＴＡＣＴＩＸ７４
２］（エポキシ当量１６０）と、 ・エポキシ樹脂エ：上記式（ｃ）で表される多官能樹脂
［東都化成株式会社製、商品名ＹＤＰＮ−６３８Ｐ］
（エポキシ当量１８０）と、 ・エポキシ樹脂オ：臭素化ビスフェノールＡ型エポキシ
樹脂［東都化成株式会社製、商品名ＹＤＢ４００］（エ
ポキシ当量４００）と、 ・エポキシ樹脂カ：臭素化ビスフェノールＡ型エポキシ
樹脂［東都化成株式会社製、商品名ＹＤＢ５００］（エ
ポキシ当量５００）と、を用いた。The epoxy resins used include: epoxy resin A: a polyfunctional resin represented by the above formula (a) [trade name: EPPN501H, manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 164); : Polyfunctional resin represented by the above formula (a) [trade name Epicoat 1 manufactured by Yuka Shell Epoxy Co., Ltd.]
032] (epoxy equivalent: 174); and epoxy resin c: a polyfunctional resin represented by the above formula (a) [TACTIX74 manufactured by Dow Chemical Co., Ltd.]
2] (Epoxy equivalent: 160); Epoxy resin d: polyfunctional resin represented by the above formula (c) [YDPN-638P manufactured by Toto Kasei Co., Ltd.]
(Epoxy equivalent: 180);-Epoxy resin e: brominated bisphenol A type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: YDB400] (epoxy equivalent: 400);-Epoxy resin: brominated bisphenol A type epoxy resin [ Manufactured by Toto Kasei Co., Ltd., trade name: YDB500] (epoxy equivalent: 500).

【００５４】[0054]

【表２】 [Table 2]

【００５５】[0055]

【表３】 [Table 3]

【００５６】次いで、得られたエポキシ樹脂組成物を室
温で２４時間保管した後、厚み０．１ｍｍのガラスクロ
ス［旭シュエーベル株式会社製、商品名２１１６Ｌ］に
含浸し、１４０℃で４分間乾燥して樹脂含有率６５重量
％のプリプレグを得た。Next, the obtained epoxy resin composition was stored at room temperature for 24 hours, then impregnated with a glass cloth having a thickness of 0.1 mm (trade name: 2116L, manufactured by Asahi Schwebel KK), and dried at 140 ° C. for 4 minutes. Thus, a prepreg having a resin content of 65% by weight was obtained.

【００５７】得られたプリプレグの両面に１８μｍの銅
箔［日鉱グールドフォイル株式会社製、商品名ＪＴＣ］
を配置して被圧体とし、温度１９０℃、圧力２ＭＰａの
条件で１００分加熱・加圧して両面に銅箔が接着された
積層板を得た。18 μm copper foil [trade name: JTC, manufactured by Nikko Gould Foil Co., Ltd.] on both sides of the obtained prepreg.
Was placed under pressure and heated and pressed at a temperature of 190 ° C. and a pressure of 2 MPa for 100 minutes to obtain a laminate having copper foils bonded to both surfaces.

【００５８】（実施例１４〜２１、比較例６〜１０）用
いたエポキシ樹脂として、下記のエポキシ樹脂キ〜コ
を、表４及び表５に示す割合（単位：重量部）で用いて
エポキシ樹脂組成物を得たこと以外は、実施例１〜１３
及び比較例１〜５と同様にして、エポキシ樹脂組成物、
プリプレグ及び両面に銅箔が接着された積層板を得た。Examples 14 to 21 and Comparative Examples 6 to 10 The following epoxy resins were used in the proportions (unit: parts by weight) shown in Tables 4 and 5 as the epoxy resins used. Examples 1-13 except that the composition was obtained
And in the same manner as in Comparative Examples 1 to 5, an epoxy resin composition,
A prepreg and a laminate having copper foil adhered to both surfaces were obtained.

【００５９】用いたエポキシ樹脂としては、 ・エポキシ樹脂キ：上記式（ｂ）で表される多官能樹脂
［油化シェルエポキシ株式会社製、商品名ＥＰＯＮ１０
３１］（エポキシ当量２１３）と、 ・エポキシ樹脂ク：上記式（ｂ）で表される多官能樹脂
［油化シェルエポキシ株式会社製、商品名Ｅｐｉｋｏｔ
ｅ１０３１］（エポキシ当量２００）と、 ・エポキシ樹脂ケ：臭素化ビスフェノールＡ型エポキシ
樹脂［東都化成株式会社製、商品名ＹＤＢ４００］（エ
ポキシ当量４００）と、 ・エポキシ樹脂コ：臭素化ビスフェノールＡ型エポキシ
樹脂［東都化成株式会社製、商品名ＹＤＢ５００］（エ
ポキシ当量５００）と、を用いた。Epoxy resins used include: epoxy resin: a polyfunctional resin represented by the above formula (b) [trade name: EPON10, manufactured by Yuka Shell Epoxy Co., Ltd.]
31] (Epoxy equivalent 213); Epoxy resin: a polyfunctional resin represented by the above formula (b) [Epikot, manufactured by Yuka Shell Epoxy Co., Ltd.]
e1031] (epoxy equivalent: 200), epoxy resin: brominated bisphenol A type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name: YDB400] (epoxy equivalent: 400), epoxy resin: brominated bisphenol A type epoxy Resin [Tokyo Kasei Co., Ltd., trade name: YDB500] (epoxy equivalent: 500) was used.

【００６０】[0060]

【表４】 [Table 4]

【００６１】[0061]

【表５】 [Table 5]

【００６２】（評価、結果）得られたエポキシ樹脂組成
物の、初期粘度及び保存性を評価した。初期粘度の測定
は、Ｂ型粘度計を用いて２５℃で測定し、５００ｃｐｓ
以下の場合を良好（○）とし、５００ｃｐｓを越える場
合を不良（×）とした。また、保存性の測定は、２５℃
で２４時間保存した後、初期粘度と同様にして測定及び
判定を行った。(Evaluation and Results) The initial viscosity and storage stability of the obtained epoxy resin composition were evaluated. The initial viscosity was measured at 25 ° C. using a B-type viscometer and measured at 500 cps.
The following cases were evaluated as good (○), and the cases exceeding 500 cps were evaluated as poor (x). In addition, the measurement of the storage stability
After storing for 24 hours, measurement and determination were performed in the same manner as in the initial viscosity.

【００６３】その結果は表２〜表５に示したように、各
実施例及び比較例１，３，５，６，８，１０で得られた
エポキシ樹脂組成物は初期粘度も小さく、析出現象もな
く保存性に優れていたが、数平均分子量１７０００の変
成フェノール生成物（Ｆ）を用いた比較例２，４，７及
び９は、初期粘度、保存性とも劣ることが確認された。As shown in Tables 2 to 5, the epoxy resin compositions obtained in Examples and Comparative Examples 1, 3, 5, 6, 8, and 10 had low initial viscosities and precipitation phenomena. Comparative Examples 2, 4, 7 and 9 using the modified phenol product (F) having a number average molecular weight of 17000 were inferior in both the initial viscosity and the storage stability.

【００６４】また、得られたプリプレグの、外観、取り
扱い性及び含浸性を評価した。外観は、スジ状や垂れた
形状の外観不具合部の有無を目視で観察し、無しの場合
を良好（○）、有りの場合を不良（×）とした。また、
取り扱い性は、プリプレグを１８０度折り曲げ、樹脂の
脱離の有無を目視で観察し、無しの場合を良好（○）、
有りの場合を不良（×）とした。また、含浸性は、切断
面を１０００倍でＳＥＭ観察し、内部に気泡が無い場合
を良好（○）、わずかに有る場合を△、多数有る場合を
不良（×）とした。The appearance, handleability and impregnation of the obtained prepreg were evaluated. The external appearance was visually observed for the presence or absence of a streak-like or sagging external appearance defect, and the absence was evaluated as good (○), and the existence was evaluated as poor (x). Also,
The handleability was determined by bending the prepreg by 180 degrees and visually observing the presence or absence of resin detachment.
When there was, it was determined to be defective (x). The impregnating property was evaluated by SEM observation of the cut surface at a magnification of 1000 times. Good results were obtained when there were no air bubbles inside (o), poor when there were a few bubbles, and poor (x) when there were many bubbles.

【００６５】その結果は表２〜表５に示したように、実
施例１〜１３及び比較例１，３，５で得られたプリプレ
グは、比較例２及び４と比較して、また、実施例１４〜
２４及び比較例６，８，１０で得られたプリプレグは、
比較例７及び９と比較して、外観、取り扱い性及び含浸
性が優れることが確認された。As shown in Tables 2 to 5, the prepregs obtained in Examples 1 to 13 and Comparative Examples 1, 3, and 5 were compared with Comparative Examples 2 and 4, and Example 14-
24 and the prepregs obtained in Comparative Examples 6, 8, and 10
It was confirmed that the appearance, the handleability, and the impregnation were superior to Comparative Examples 7 and 9.

【００６６】また、変成フェノール生成物の数平均分子
量が、１０００〜３０００の範囲内である実施例１〜８
及び実施例１１〜１３は、実施例９，１０と比較して、
また、実施例１４〜２１及び実施例２４は、実施例２
２，２３と比較して、含浸性が特に優れることが確認さ
れた。Examples 1 to 8 in which the number average molecular weight of the modified phenol product is in the range of 1,000 to 3,000
And Examples 11-13 are compared with Examples 9 and 10,
Examples 14 to 21 and Example 24 correspond to Example 2
It was confirmed that the impregnating property was particularly excellent as compared with 2,23.

【００６７】また、得られた積層板の、誘電率、誘電正
接、はんだ耐熱性、銅箔の引きはがし強さ、及び、銅箔
とボンディングワイヤーとの接着強度の評価としてワイ
ヤープル強度を測定した。誘電率及び誘電正接の測定
は、ＭＩＬ規格に基づき測定した。はんだ耐熱性及び引
きはがし強さは、ＪＩＳ規格Ｃ６４８１に基づき測定し
た。The obtained laminate was measured for the dielectric constant, the dielectric loss tangent, the solder heat resistance, the peeling strength of the copper foil, and the wire pull strength as an evaluation of the bonding strength between the copper foil and the bonding wire. . The dielectric constant and the dielectric loss tangent were measured based on the MIL standard. Solder heat resistance and peel strength were measured based on JIS standard C6481.

【００６８】ワイヤープル強度は、カイジョー社製のワ
イヤーボンダー［商品名ＦＢ−１１８Ａ］を用いて、φ
３０μｍの金線［田中貴金属工業株式会社製］を積層板
表面の銅箔に接合した後、Ｄａｇｅ社製のボンドテスタ
ー［商品名ＢＴ２２］を用いて、温度１８０℃、ヘッド
スピード０．３ｍｍ／秒の条件で、金線が剥がれる強度
を測定した。The wire pull strength was measured using a wire bonder (trade name: FB-118A) manufactured by Kaijo Co., Ltd.
After bonding a 30 μm gold wire [manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.] to the copper foil on the surface of the laminate, using a Dage bond tester [trade name BT22], a temperature of 180 ° C. and a head speed of 0.3 mm / sec. Under the conditions described above, the strength at which the gold wire was peeled was measured.

【００６９】その結果は表２〜表５に示したように、実
施例１〜１３で得られた積層板は、多官能樹脂を含有し
ない比較例１〜３と比較して、また、実施例１４〜２４
で得られた積層板は、同様の比較例６〜８と比較して、
ワイヤープル強度が優れることが確認された。As shown in Tables 2 to 5, the laminates obtained in Examples 1 to 13 were compared with Comparative Examples 1 to 3 containing no polyfunctional resin. 14-24
The laminate obtained in the above, compared with the same Comparative Examples 6 to 8,
It was confirmed that the wire pull strength was excellent.

【００７０】また、実施例１〜１３で得られた積層板
は、変成フェノール生成物の数平均分子量が用いたＰＰ
Ｅの数平均分子量の１０〜７０％の範囲外である比較例
２〜５と比較して、また、実施例１４〜２４で得られた
積層板は、同様の比較例７〜１０と比較して、はんだ耐
熱性が優れることが確認された。また、各実施例で得ら
れた積層板は、誘電率及び誘電正接も優れていることが
確認された。Further, the laminates obtained in Examples 1 to 13 were prepared by using the PP obtained by using the number average molecular weight of the modified phenol product.
Compared with Comparative Examples 2 to 5, which are out of the range of 10 to 70% of the number average molecular weight of E, the laminates obtained in Examples 14 to 24 are compared with the same Comparative Examples 7 to 10. As a result, it was confirmed that the solder heat resistance was excellent. In addition, it was confirmed that the laminate obtained in each of the examples had excellent dielectric constant and dielectric loss tangent.

【００７１】以上の評価結果より、各実施例は、エポキ
シ樹脂組成物特性、プリプレグ特性、積層板特性の全て
が良好であるが、各比較例は少なくとも１つの特性が劣
ることが確認された。From the above evaluation results, it was confirmed that the epoxy resin composition properties, the prepreg properties, and the laminate properties were all good in each example, but at least one property was inferior in each comparative example.

【００７２】[0072]

【発明の効果】本発明の請求項１から請求項７に係るエ
ポキシ樹脂組成物を用いると、誘電率、誘電正接及びは
んだ耐熱性を低下することなしに、その表面に有する金
属箔とボンディングワイヤーを接合した場合に、金属箔
とボンディングワイヤーとの接着強度が優れた積層板が
得られる。When the epoxy resin composition according to any one of claims 1 to 7 of the present invention is used, a metal foil and a bonding wire having on the surface thereof without lowering the dielectric constant, dielectric loss tangent and solder heat resistance. When these are bonded, a laminate having excellent adhesion strength between the metal foil and the bonding wire can be obtained.

【００７３】本発明の請求項５に係るエポキシ樹脂組成
物を用いると、上記の効果に加え、含浸性の優れたプリ
プレグが得られる。When the epoxy resin composition according to the fifth aspect of the present invention is used, a prepreg excellent in impregnation in addition to the above effects can be obtained.

【００７４】本発明の請求項８に係るプリプレグを用い
ると、誘電率、誘電正接及びはんだ耐熱性を低下するこ
となしに、その表面に有する金属箔とボンディングワイ
ヤーを接合した場合に、金属箔とボンディングワイヤー
との接着強度が優れた積層板が得られる。When the prepreg according to the eighth aspect of the present invention is used, when the metal foil on the surface and the bonding wire are joined without reducing the dielectric constant, the dielectric loss tangent, and the solder heat resistance, A laminate having excellent bonding strength with the bonding wire can be obtained.

【００７５】本発明の請求項９に係る積層板は、誘電
率、誘電正接及びはんだ耐熱性が優れると共に、その表
面に有する金属箔とボンディングワイヤーを接合した場
合に、金属箔とボンディングワイヤーとの接着強度が優
れた積層板となる。The laminate according to the ninth aspect of the present invention is excellent in dielectric constant, dielectric loss tangent, and soldering heat resistance, and when the metal foil and the bonding wire on the surface are joined together, A laminate having excellent adhesive strength is obtained.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｊ 5/24 ＣＦＣ (72)発明者 斉藤 英一郎 大阪府門真市大字門真1048番地松下電工株 式会社内──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI C08J 5/24 CFC C08J 5/24 CFC (72) Inventor Eiichiro Saito 1048 Odakadoma, Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd.

Claims (9)

【特許請求の範囲】[Claims] 【請求項１】 数平均分子量が１００００〜３００００
のポリフェニレンエーテル樹脂とフェノール性化合物を
反応開始剤の存在下で再分配反応させて、数平均分子量
が用いたポリフェニレンエーテル樹脂の数平均分子量の
５〜７０％になるように反応させた変成フェノール生成
物、エポキシ樹脂及びエポキシ樹脂の硬化剤とを含有す
るエポキシ樹脂組成物において、エポキシ樹脂として、
分子内にエポキシ基を３個以上有するエポキシ樹脂を含
有することを特徴とするエポキシ樹脂組成物。1. A compound having a number average molecular weight of 10,000 to 30,000
Polyphenolene ether resin and a phenolic compound are redistributed in the presence of a reaction initiator to form a modified phenol in which the number average molecular weight is reacted so as to be 5 to 70% of the number average molecular weight of the used polyphenylene ether resin. In an epoxy resin composition containing a product, an epoxy resin and a curing agent for the epoxy resin, as the epoxy resin,
An epoxy resin composition comprising an epoxy resin having three or more epoxy groups in a molecule. 【請求項２】 分子内にエポキシ基を３個以上有するエ
ポキシ樹脂を、全エポキシ樹脂１００重量部中に１〜４
０重量部含有することを特徴とする請求項１記載のエポ
キシ樹脂組成物。2. An epoxy resin having three or more epoxy groups in a molecule is contained in an amount of 1 to 4 per 100 parts by weight of the total epoxy resin.
The epoxy resin composition according to claim 1, wherein the epoxy resin composition contains 0 parts by weight. 【請求項３】 分子内にエポキシ基を３個以上有するエ
ポキシ樹脂として、下記式（ａ）で表されるエポキシ樹
脂を含有することを特徴とする請求項１又は請求項２記
載のエポキシ樹脂組成物。 【化１】 3. The epoxy resin composition according to claim 1, wherein the epoxy resin having three or more epoxy groups in the molecule contains an epoxy resin represented by the following formula (a). Stuff. Embedded image 【請求項４】 分子内にエポキシ基を３個以上有するエ
ポキシ樹脂として、下記式（ｂ）で表されるエポキシ樹
脂を含有することを特徴とする請求項１又は請求項２記
載のエポキシ樹脂組成物。 【化２】 4. The epoxy resin composition according to claim 1, wherein the epoxy resin having three or more epoxy groups in the molecule contains an epoxy resin represented by the following formula (b). Stuff. Embedded image 【請求項５】 変成フェノール生成物の数平均分子量
が、１０００〜３０００であることを特徴とする請求項
１から請求項４のいずれかに記載のエポキシ樹脂組成
物。5. The epoxy resin composition according to claim 1, wherein the modified phenol product has a number average molecular weight of 1,000 to 3,000. 【請求項６】 反応開始剤が、過酸化ベンゾイルである
ことを特徴とする請求項１から請求項５のいずれかに記
載のエポキシ樹脂組成物。6. The epoxy resin composition according to claim 1, wherein the reaction initiator is benzoyl peroxide. 【請求項７】 フェノール性化合物が、分子内に２個以
上のフェノール性水酸基を有するフェノール性化合物で
あることを特徴とする請求項１から請求項６のいずれか
に記載のエポキシ樹脂組成物。7. The epoxy resin composition according to claim 1, wherein the phenolic compound is a phenolic compound having two or more phenolic hydroxyl groups in a molecule. 【請求項８】 請求項１から請求項７のいずれかに記載
のエポキシ樹脂組成物を、基材に含浸乾燥してなるプリ
プレグ。8. A prepreg obtained by impregnating and drying a substrate with the epoxy resin composition according to any one of claims 1 to 7. 【請求項９】 請求項８記載のプリプレグに金属箔を重
ね、加熱・加圧してなる積層板。9. A laminate obtained by laminating a metal foil on the prepreg according to claim 8, and heating and pressing the laminate.
JP07813197A 1997-02-24 1997-03-28 Epoxy resin composition, prepreg and laminate Expired - Lifetime JP3570147B2 (en)

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Application Number Priority Date Filing Date Title
JP9-38787 1997-02-24
JP3878797 1997-02-24
JP07813197A JP3570147B2 (en) 1997-02-24 1997-03-28 Epoxy resin composition, prepreg and laminate

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JP3570147B2 JP3570147B2 (en) 2004-09-29

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081445A1 (en) * 2000-04-21 2001-11-01 Mitsubishi Rayon Co., Ltd. Epoxy resin composition and prepreg made with the epoxy resin composition
JP2002067176A (en) * 2000-08-29 2002-03-05 Mitsubishi Rayon Co Ltd Tubular body made of fiber reinforced resin
JP2010235933A (en) * 2009-03-09 2010-10-21 Panasonic Electric Works Co Ltd Transparent film
JP2017190423A (en) * 2016-04-15 2017-10-19 南亞塑膠工業股▲分▼有限公司 Polyphenylene ether modified phenol benzaldehyde polyfunctional epoxy resin and use thereof
TWI624506B (en) * 2013-12-16 2018-05-21 南韓商三星電機股份有限公司 Insulating resin composition for printed circuit board and products manufactured by using the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081445A1 (en) * 2000-04-21 2001-11-01 Mitsubishi Rayon Co., Ltd. Epoxy resin composition and prepreg made with the epoxy resin composition
US6838176B2 (en) 2000-04-21 2005-01-04 Mitsubishi Rayon Co., Ltd. Epoxy resin composition and prepreg made with the epoxy resin composition
JP2002067176A (en) * 2000-08-29 2002-03-05 Mitsubishi Rayon Co Ltd Tubular body made of fiber reinforced resin
JP2010235933A (en) * 2009-03-09 2010-10-21 Panasonic Electric Works Co Ltd Transparent film
TWI624506B (en) * 2013-12-16 2018-05-21 南韓商三星電機股份有限公司 Insulating resin composition for printed circuit board and products manufactured by using the same
JP2017190423A (en) * 2016-04-15 2017-10-19 南亞塑膠工業股▲分▼有限公司 Polyphenylene ether modified phenol benzaldehyde polyfunctional epoxy resin and use thereof

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